Charged cyclodextrin polymer material, method for producing the same, and method for using the same

Abstract

To provide an electrically charged cyclodextrin polymer material, as well as a method for producing and using the same. [Solution] This disclosure relates to charged polymer materials for purifying fluid samples from trace contaminants such as anionic trace contaminants, and to methods for using them. The present invention provides charged cyclodextrin polymer materials, as well as methods for producing and using them. In some embodiments, this disclosure provides products comprising the porous polymer material of this disclosure or supported porous polymer material.

Description

Background Art

[0001] As a result of human activities, organic micropollutants (MPs) exist in water resources at concentrations of ng / L 14,15 ~μg / L -1 . Due to concerns about the adverse effects on human health 1,2 and the environment 3~7 , the development of technologies for more effectively removing MPs is underway 8~10 . The physicochemical properties of MPs, such as surface charge, size, and chemical functionality, vary widely. Charged MPs can be cationic, anionic, or zwitterionic, and it is usually difficult to remove them using conventional adsorption methods such as activated carbon in the presence of complex matrix components such as natural organic matter (NOM). Among anionic MPs, PFAS has become a particular environmental concern due to its correlation with resistance to biodegradation and adverse health effects. PFAS is used in the formulation of thousands of consumer products 11~16 and is included in aqueous foam formulations used to suppress aviation fires in training scenarios 1 . As a result, PFAS has contaminated surface and groundwater near thousands of airports and military facilities 18,19 . In 2016, Hu and co-workers showed that at least 6 million Americans were provided with drinking water contaminated with PFAS above the health advisory limit of 70 ng / L for perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) by the US Environmental Protection Agency in 2016 20 . PFAS has been shown to be associated with cancer -1 , liver damage 21 , thyroid disease 3 , and other health problems 4 5 . 6 23,24 .

[0002] Contaminated water systems are usually improved by granular activated carbon (GAC), but this is an expensive and temporary solution because of its low affinity for PFAS, especially short-chain derivatives 23,24 . In recent reports 14,15It was discovered that non-covalent interactions and static electricity of functional groups influence the affinity of PFAS to the adsorbent. For example, the combination of fluorophilic interactions of the crosslinking agent and low concentrations of anionically charged functional groups in decafluorobiphenyl-crosslinked CDP resulted in higher removal rates of PFOA and PFOS from water. In contrast, CDP crosslinked with epichlorohydrin showed lower PFAS removal rates. 25 .

[0003] Adsorption processes can be used to remove specific contaminants or classes of contaminants from fluids such as air and water. Activated carbon (AC) is the most widely used adsorbent for removing organic contaminants, and its effectiveness stems primarily from its high surface area, nanostructured pores, and hydrophobicity. However, not all types of AC can effectively remove all contaminants, particularly anionic MPs. Due to the ambiguous definitions of their structures and binding site variations, optimal adsorption selectivity requires empirical screening in new equipment, making rational design and improvement difficult. Furthermore, regenerating spent AC is energy-intensive (heating to 500-900°C or other energy-intensive procedures), and full performance is not restored. AC also has a slow rate of contaminant uptake, reaching its uptake equilibrium in hours to days, meaning that more rapid contaminant removal requires excess adsorbent. Finally, AC may not perform well against many new contaminants, especially relatively hydrophilic ones.

[0004] Alternative adsorbents can be produced from polymeric cyclodextrin materials derived from insoluble polymers of β-cyclodextrin (β-CD). This material is a toroidal macrocyclic compound composed of seven glucose units, with internal cavities capable of binding to organic compounds. β-CD is an inexpensive and sustainably produced monomer derived from corn starch and is widely used in the formulation and stabilization of pharmaceuticals, flavorings, and fragrances, as well as in the stationary phase of chiral chromatography. Insoluble β-CD polymers are formed by crosslinking epichlorohydrin with other reactive compounds, and have clearly defined binding sites and It is characterized by a high association constant. Insoluble β-CD polymers crosslinked with epichlorohydrin are being considered as a substitute for AC for water purification, but their small surface area results in inferior adsorption performance compared to AC.

[0005] Therefore, there is a need for a new adsorbent that overcomes the shortcomings of AC and other adsorbents and provides more effective adsorption and / or sequestration properties for MPs (such as anionic MPs). There is a need for an adsorbent that provides rapid extraction of anionic MPs, high total uptake, and easy regeneration and reuse procedures. The present invention satisfies these requirements. [Overview of the project] [Means for solving the problem]

[0006] In some embodiments, this disclosure relates to formula (I): [ka] The present invention provides a porous polymer material containing multiple cyclodextrins crosslinked by multiple crosslinks having multiple crosslinks, During the ceremony, A is an aryl or heteroaryl moiety, Each R 1 These are H, C1-C6 alkyl, C1-C3 haloalkyl, aryl, heteroaryl, -CF3, -SO3H, -CN, -NO2, -NH2, -NCO, -C(O)2R 3 ,-C(O)N(R 3 )2, and -halogens are independently selected from the group, Each R 2 These are independently H, -OH, -O-metal cation, alkyl, aryl, heteroaryl, -SH, -S-metal cation, -S-alkyl, -C(O)2H, or -C(O)NH2. Each R 3 These are independently -H, -C1~C6 alkyl, -C1~C3 haloalkyl, aryl, and -C(O)N(R) a )(R b ), -C(O)Rc , -CO2R c , -SO2N(R a )(R b ), or -SOR c And each R a and R b These are independently H or C1-C6 alkyl groups. Each W independently consists of a bond, an alkylene group, an arylene group, a heteroarylene group, -O-arylene-, and -(CH2). a -Arirene-, -SO2-Arirene-, -NH-Arirene-, -S-Arirene-, -O-Heteroarirene-, -(CH2) a -heteroarylene-, -SO2-heteroarylene-, -NH-heteroarylene-, -S-heteroarylene-, -(-O-(CH2) a -) x -,-(-NH-(CH2) a -) x -,-(-S-(CH2) a -) x -, [ka] There, a is between 0 and 100, x is between 1 and 100, and each arylene or heteroarylene moiety may be substituted or unsubstituted. Each Z is either a cationic or anionic moiety. Each L independently consists of -O-, -S-, -N-, substituted or unsubstituted alkylenes of C1-C6, and haloalkylenes of C1-C3. [ka] A connecting part selected from the group consisting of, A' is a covalent bond to A, Z' is a covalent bond to Z, *teeth, [ka] It is a covalent bond to, [ka] These are binding sites to multiple cyclodextrin carbon atoms, x ranges from 0 to 8. y1 is 1 to 4, y2 is between 1 and 4. y3 is between 0 and 4.

[0007] In some embodiments, crosslinking of porous polymer materials is performed using formula (II): [ka] It has, During the ceremony, y2 is either 1 or 2. x is either 1 or 2.

[0008] In some embodiments, the porous polymer material of the present disclosure is a material of formula (III): [ka] Includes multiple linkers, In the formula, one R 4 is -H and one R 4 It is -Me.

[0009] In some embodiments, the Disclosure provides a supported porous polymer material comprising porous particles immobilized on a solid substrate, wherein the porous particles comprise a plurality of cyclodextrin moieties together with a plurality of crosslinks comprising formulas (I), (II), or (III).

[0010] In some embodiments, the Disclosure provides a method for purifying a fluid sample containing one or more contaminants, the method comprising contacting the fluid sample with a porous polymer material of the Disclosure or a supported porous polymer material, thereby adsorbing at least 50% by weight of the total amount of one or more contaminants in the fluid sample onto the porous polymer material.

[0011] In some embodiments, the Disclosure provides a method for removing one or more compounds from a fluid sample or determining the presence or absence of one or more compounds in a fluid sample, the method comprising: a) contacting a sample with a porous polymer material or supported porous polymer material of the Disclosure over an incubation period; b) separating the porous polymer material or supported porous polymer material from the sample after the incubation period; c) heating the porous polymer material or supported porous polymer material separated in step b) or contacting the porous polymer material or supported porous polymer material separated in step b) with a solvent to release at least a portion of the compounds from the porous polymer material or supported porous polymer material; d1) optionally isolating at least a portion of the compounds released in step c), or d2) determining the presence or absence of the compounds released in step c), wherein the presence of one or more compounds correlates with the presence of one or more compounds in a sample.

[0012] In some embodiments, the Disclosure provides products comprising the porous polymer material of the Disclosure or a supported porous polymer material. [Brief explanation of the drawing]

[0013] [Figure 1] The images show a comparison of the PFAS uptake capabilities of the polymers of this disclosure at 0.5 hours (top) and 48 hours (bottom). [Figure 2] The top and bottom images show a comparison of PFOA incorporation and PFOS incorporation between two choline chloride-modified TFN-CDP polymers and one β-CD-TDI polymer. [Figure 3] The 1H NMR spectra of β-CD-TDI polymer (top) and β-CD (bottom) are shown. [Figure 4] This shows the change in the 1H NMR spectrum of the β-CD-TDI polymer when D2O is added. [Figure 5]This paper compares different β-CD-TDI polymers prepared using different molar equivalents of β-CD:TDI. [Figure 6-1] This paper compares choline chloride-modified β-CD-TDI polymers prepared using different molar equivalents of choline chloride. [Figure 6-2] This paper compares choline chloride-modified β-CD-TDI polymers prepared using different molar equivalents of choline chloride. [Figure 7] The image shows the incorporation of choline chloride-modified β-CD-TFN using methylene blue (top) and methyl orange (bottom). [Figure 8] The isotherms of MO incorporation for modified TFN-CDP polymers containing 1.5 (top) and 3.0 (center) equivalents of choline chloride, and for unmodified TFN-CDP (bottom), are shown. Each point represents an experimental data point, and each straight line is a curve fitted using the Langmuir model. [Figure 9] The BPA incorporation isotherms for modified TFN-CDP polymers containing 1.5 (top) and 3.0 (center) equivalents of choline chloride, and for unmodified TFN-CDP (bottom), are shown. Each point represents an experimental data point, and each straight line is a curve fitted using the Langmuir model. [Figure 10] The 1H NMR spectrum of a choline chloride-modified β-CD-TDI polymer prepared using a molar equivalent ratio of 1:6:1 β-CD:TDI:choline chloride is shown. [Figure 11] A comparison of choline chloride-modified β-CD-TDI polymers and β-CD-TDI polymers is shown. [Figure 12] This shows a comparison between choline chloride-modified β-CD-TDI polymers with different amounts of choline chloride added. [Figure 13] This shows the PFOA uptake rate of choline chloride-modified β-CD-TDI polymer. [Modes for carrying out the invention]

[0014] All documents cited herein are invoked by reference in whole for any purpose, just as each individual document is indicated to be specifically and individually invoked by reference.

[0015] Where used above and throughout this disclosure, the following terms shall be understood to have the following meanings unless otherwise indicated. Where a term is not used, the prior art terms known to those skilled in the art shall prevail.

[0016] As used herein, the terms “including,” “containing,” and “comprising” are used in an open, non-restrictive sense.

[0017] In this disclosure, the articles "a" and "an" are used to refer to one or more (i.e., at least one) grammatical objects of the article. For example, "an element" means one or more elements.

[0018] Unless otherwise indicated, the term "and / or" is used in this disclosure to mean either "and" or "or".

[0019] For the sake of brevity, some of the quantitative expressions expressed herein are not modified by the term “approximately.” Whether the term “approximately” is explicitly used or not, all quantities expressed herein are intended to mean actual given values, and also to mean approximations to such given values ​​that can be reasonably inferred on the basis of the ordinary skill of the art, including equivalent and approximate values ​​to such given values ​​under experimental and / or measurement conditions. Whenever a yield is expressed as a percentage, such a yield is the same actual yield that can be obtained under specific stoichiometric conditions. This refers to the mass of the substance for which the yield is given relative to the maximum amount of the substance. Unless otherwise specified, concentrations expressed as percentages refer to mass ratios.

[0020] The terms "adsorbent" or "adsorbing" are used to refer to compositions or methods of the present disclosure and to solid materials described herein that remove impurities or contaminants, typically organic molecules, from a fluid medium such as a liquid (e.g., water) or a gas (e.g., air or other commercially useful gases such as nitrogen, argon, helium, carbon dioxide, or anesthetic gases). Such terms do not imply any particular physical mechanism (e.g., adsorption and absorption).

[0021] The term "cyclodextrin" includes any known cyclodextrins, particularly unsubstituted cyclodextrins containing 6 to 12 glucose units, such as α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and / or their derivatives and / or mixtures thereof. α-cyclodextrin consists of 6 glucose units, β-cyclodextrin consists of 7 glucose units, and γ-cyclodextrin consists of 8 glucose units, with the glucose units arranged in a donut-shaped ring. The specific bonding and conformation of the glucose units give cyclodextrins a rigid conical molecular structure with a hollow interior of a specific volume. The "lining" of each internal cavity is formed by hydrogen atoms and glycoside-bridged oxygen atoms, thereby making this surface relatively hydrophobic. Due to the unique shape and physicochemical properties of the cavities, cyclodextrin molecules can absorb (form inclusion complexes of) organic molecules or parts of organic molecules that fit into the cavities.

[0022] Unless otherwise specified, the terms “crosslinking agent,” “crosslinking,” or “linker” refer to monomers that can react with one or more cyclodextrins or polymers, or form covalent bonds between them. For example, when a crosslinking agent reacts at the end of a polymer chain, it can react covalently with one cyclodextrin moiety of the polymer (e.g., via the glycoside oxygen of the cyclodextrin). A crosslinking agent may or may not react further with other monomers or cyclodextrin units or polymer chains to, for example, extend a polymer chain or link two or more polymer chains together. For example, a crosslinking agent can bond to one, two, three, or four or more monomers or cyclodextrin units or polymers.

[0023] The term "cationic moiety" refers to a group having a positive charge (e.g., +1, +2, etc.), such as ammonium, mono, di or trialkylammonium, dialkylsulfonium, and trialkylphosphonium.

[0024] The term "anionic moiety" refers to a group having a negative charge (e.g., -1, -2, etc.), such as phosphoric acid, carboxylic acids, alkoxides, and sulfuric acid.

[0025] As used herein, "alkyl" means a linear or branched saturated chain having 1 to 10 carbon atoms. Typical saturated alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1-propyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, and longer alkyl groups such as heptyl and octyl. Alkyl groups may be unsubstituted or substituted. Alkyl groups having three or more carbon atoms may be linear or branched. As used herein, "lower alkyl" means alkyl groups having one to six carbon atoms.

[0026] The term "alkylene" refers to linear and branched alkylene groups. Typical alkylene groups include, for example, methylene (-CH2-), ethylene (-CH2CH2-), propylene (-CH2CH2CH2-), isopropylene (-CH(CH3)CH2-), n-butylene (-CH2CH2CH2CH2-), and sec-butylene (-CH(CH2CH3)CH2-).

[0027] The term "hydroxyl" or "hydroxy" refers to the OH group.

[0028] Furthermore, it should be noted that any carbon and heteroatoms with unfulfilled valencies in the text, schemes, examples, and tables of this specification are assumed to have a sufficient number of hydrogen atoms to satisfy their valency.

[0029] The term "halo" or "halogen" refers to fluorine, chlorine, bromine, or iodine.

[0030] As used herein, the term "cyano" refers to a substituent having a carbon atom bonded to a nitrogen atom by a triple bond, i.e., C≡N.

[0031] As used herein, the terms “amine” or “amino” mean substituents having at least one nitrogen atom. Specifically, the terms “amino” include NH2, -NH(alkyl) or alkylamino, -N(alkyl)2 or dialkylamino, amide, carboxamide, urea, and sulfamide substituents.

[0032] Unless otherwise specifically defined, the term “aryl” refers to a cyclic aromatic hydrocarbon group having one to three aromatic rings, including monocyclic or bicyclic groups such as phenyl, biphenyl, or naphthyl. If two aromatic rings (e.g., bicyclic) are present, the aromatic rings of the aryl group may be bonded at one point (e.g., biphenyl) or condensed (e.g., naphthyl). Furthermore, in connection with this disclosure, the term aryl is interpreted as referring to two aryl rings linked by a short linker such as -CH2-, CR2- (where R may be H, alkyl, etc.), -SO2-, -SO-, -NR- (where R may be H, alkyl, etc.), or -O-, for example, aryl may refer to methylenediphenyl or oxybisphenyl, respectively. The aryl group may be optionally substituted with one or more substituents (e.g., one to five substituents) at any bonding site. Substituents may be optionally substituted themselves. Furthermore, when comprising two fused rings, the aryl groups as defined herein may have an unsaturated or partially saturated ring fused with a fully saturated ring. Exemplary ring systems of these aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl, anthracenyl, phenalenyl, phenantrenyl, indanyl, indenyl, tetrahydronaphthalenyl, and tetrahydrobenzoanurenyl.

[0033] Unless otherwise specifically defined, “heteroaryl” means a 5-18 ring-atom monovalent monocyclic or polycyclic aromatic radical, or polycyclic aromatic radical, containing one or more ring heteroatoms selected from N, O, or S, with the remaining ring atoms being C. Heteroaryl as defined herein also means a polycyclic (e.g., bicyclic) heteroaromatic group in which the heteroatoms are selected from N, O, or S. Aromatic radicals are independently optionally substituted with one or more substituents as described herein. Substituents may optionally be... The substitution itself may also be used. Examples, though not limited to these, include benzothiophene, furyl, thienyl, pyrrolyl, pyridyl, pyrazinyl, pyrazolyl, pyridadinyl, pyrimidinyl, imidazolyl, isoxazolyl, oxazolyl, oxadiazolyl, pyrazinyl, indolyl, thiophen-2-yl, quinolyl, benzopyranil, isothiazolyl, thiazolyl, thiadiazolyl, thieno[3,2-b]thiophene, Triazolyl, triazinyl, imidazo[1,2-b]pyrazolyl, furo[2,3-c]pyridinyl, imidazo[1,2-a]pyridinyl, indazolyl, pyrrolo[2,3-c]pyridinyl, pyrrolo[3,2-c]pyridinyl, pyrazolo[3,4-c]pyridinyl, benzimidazolyl, thieno[3,2-c]pyridinyl, thieno[2,3-c]pyridinyl, thieno[2,3-b]pyridinyl, benzothiazo Ryl, indolyl, indolinyl, indolinonyl, dihydrobenzothiophenyl, dihydrobenzofuranyl, benzofuran, chromanil, thiochromanil, tetrahydroquinolinyl, dihydrobenzothiazine, dihydrobenzooxanil, quinolinyl, isoquinolinyl, 1,6-naphthilidinyl, benzo[de]isoquinolinyl, pyrido[4,3-b][1,6]naphthilidinyl, thieno[2,3-b] Pyrazinyl, quinazolinyl, tetrazolo[1,5-a]pyridinyl, [1,2,4]triazolo[4,3-a]pyridinyl, isoindolyl, pyrrolo[2,3-b]pyridinyl, pyrrolo[3,4-b]pyridinyl, pyrrolo[3,2-b]pyridinyl, imidazo[5,4-b]pyridinyl, pyrrolo[1,2-a]pyrimidinyl, tetrahydropyrrolo[1,2-a]pyrimidinyl, 3,4-dihydro-2H-1λ 2-Pyrrolo[2,1-b]pyrimidine, dibenzo[b,d]thiophene, pyridine-2-one, flo[3,2-c]pyridinyl, flo[2,3-c]pyridinyl, 1H-pyrido[3,4-b][1,4]thiadinyl, benzoxazolyl, benzoisoxazolyl, flo[2,3-b]pyridinyl, benzothiophenyl, 1,5-naphthilidinyl, flo[3,2-b]pyridine, [1,2,4]triazolo[1,5-a]pyridinyl, benzo[1,2,3]triazolyl, imidazo[1,2-a]pyrimidinyl, [1,2,4]tri Examples include azolo[4,3-b]pyridazinyl, benzo[c][1,2,5]thiadiazolyl, benzo[c][1,2,5]oxadiazole, 1,3-dihydro-2H-benzo[d]imidazole-2-one, 3,4-dihydro-2H-pyrazolo[1,5-b][1,2]oxazinyl, 4,5,6,7-tetrahydropyrazolo[1,5-a]pyridinyl, thiazolo[5,4-d]thiazolyl, imidazo[2,1-b][1,3,4]thiadiazolyl, thieno[2,3-b]pyrrolyl, 3H-indolyl, and derivatives thereof. Furthermore, if comprising two fused rings, the heteroaryl group as defined herein may have an unsaturated or partially saturated ring fused with a fully saturated ring.

[0034] Numerical ranges used herein are intended to include consecutive integers unless otherwise specified. For example, a range expressed as "0 to 5" includes 0, 1, 2, 3, 4, and 5.

[0035] This disclosure provides porous (e.g., microporous or mesoporous), generally high-surface-area cyclodextrin polymer materials (P-CDPs), and methods for producing and using these materials. P-CDPs consist of insoluble polymers of cyclodextrins, which are macrocyclic compounds of glucose produced in an inexpensive and sustainable manner. The cyclodextrin polymers are crosslinked with linking groups described herein. The cyclodextrin polymers consist of cyclodextrin moieties derived from cyclodextrins. The cyclodextrin moieties can be derived from naturally occurring cyclodextrins (e.g., α-, β-, and γ-, each containing 6, 7, and 8 glucose units) or synthetic cyclodextrins. The cyclodextrin moieties have at least one -O- bond derived from an -OH group on the cyclodextrin from which the cyclodextrin moiety is derived. The cyclodextrin portion can contain 3 to 20 glucose units (including all ranges between those values), and can be 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 It contains 13, 14, 15, 16, 17, 18, 19, and 20 glucose units. In many embodiments, the cyclodextrin moiety is derived from starch and contains 6 to 9 glucose units. The polymer material may contain two or more different cyclodextrin moieties. In certain embodiments, P-CDP is composed of an insoluble polymer of β-cyclodextrin (β-CD).

[0036] P-CDP may also contain cyclodextrin derivatives or modified cyclodextrins. Cyclodextrin derivatives are mainly composed of molecules in which some of the OH groups are converted to OR groups. Cyclodextrin derivatives may have one or more additional parts that provide further functionality, such as desirable solubility behavior and affinity properties. Examples of suitable cyclodextrin derivative materials include methylated cyclodextrins (e.g., RAMEB, randomly methylated β-cyclodextrin), hydroxyalkylated cyclodextrins (e.g., hydroxypropyl-β-cyclodextrin and hydroxypropyl-γ-cyclodextrin), acetylated cyclodextrins (e.g., acetyl-γ-cyclodextrin), reactive cyclodextrins (e.g., chlorotriazinyl-β-CD), branched cyclodextrins (e.g., glucosyl-β-cyclodextrin and maltosyl-β-cyclodextrin), sulfobutyl-β-cyclodextrin, and sulfated cyclodextrins. For example, the cyclodextrin portion further includes a portion that binds (e.g., specifically) to a metal such as arsenic, cadmium, copper, or lead.

[0037] P-CDP is also a cyclodextrin derivative having a short-chain alkyl group, such as methylated cyclodextrin and ethylated cyclodextrin, where R is a methyl group or an ethyl group; or R is -CH2-CH(OH)-CH3 or - Cyclodextrins having a hydroxy substituent such as hydroxypropyl cyclodextrin and / or hydroxyethyl cyclodextrin, where R is CH2CH2-OH; branched cyclodextrins such as maltose-bonded cyclodextrin; cationic cyclodextrins such as those containing 2-hydroxy-3-(dimethylamino)propyl ether, where R is CH2-CH(OH)-CH2-N(CH3)2, which is cationic at low pH; and cyclodextrins where R is CH2-CH(OH)-CH2-N + (CH3)3Cl -These include, for example, quaternary ammonium compounds such as 2-hydroxy-3-(trimethylammonio)propyl ether chloride group; anionic cyclodextrins such as carboxymethyl cyclodextrin, cyclodextrin sulfate, and succinyl cyclodextrin; and amphoteric cyclodextrins such as carboxymethyl / quaternary ammonium cyclodextrin. ("Optimal Performances with Minimal Chemical Modification of Cyclodextrins", F. Diedaini-Pilard and B. Perly, The 7th International Cyclodextrin Symposium) The invention may also include cyclodextrin derivatives such as those disclosed in U.S. Patent No. 6,881,712, which include cyclodextrins having a 3-6-anhydrocyclomalto structure in at least one glucopyranose unit, such as mono-3-6-anhydrocyclodextrin, and mixtures thereof, as disclosed in Abstracts, April 1994, p. 49 (referencing the above reference). Other cyclodextrin derivatives include U.S. Patent No. 3,426,011 by Parmerter et al., issued on February 4, 1964; U.S. Patents No. 3,453,257, No. 3,453,258, No. 3,453,259, and No. 3,453,260, all issued on July 1, 1969, all in the name of Parmerter et al.; and U.S. Patent No. 3,459,731 by Gramera et al., issued on August 5, 1969. ; U.S. Patent No. 3,553,191 by Parmerter et al., issued January 5, 1971; U.S. Patent No. 3,565,887 by Parmerter et al., issued February 23, 1971; U.S. Patent No. 4,535,152 by Szejtli, issued August 13, 1985; U.S. Patent No. 4,616,008 by Hirai et al., issued October 7, 1986; U.S. Patent No. 4,616,008 by Ogino et al., issued July 7, 1987 U.S. Patent No. 4,678,598; U.S. Patent No. 4,638,058 by Brandt et al., issued January 20, 1987; and U.S. Patent No. 4,746,734 by Tsuchiyama et al., issued May 24, 1988, both of which are incorporated herein by reference.

[0038] In some embodiments, this disclosure relates to formula (I): [ka] A porous polymer material is provided which contains multiple cyclodextrins crosslinked by multiple crosslinks having multiple crosslinks, During the ceremony, A is an aryl or heteroaryl moiety, Each R 1 These are H, C1-C6 alkyl, C1-C3 haloalkyl, aryl, heteroaryl, -CF3, -SO3H, -CN, -NO2, -NH2, -NCO, -C(O)2R 3 ,-C(O)N(R 3 )2, and -halogens are independently selected from the group, Each R 2 These are independently H, -OH, -O-metal cation, alkyl, aryl, heteroaryl, -SH, -S-metal cation, -S-alkyl, -C(O)2H, or -C(O)NH2. Each R 3 These are independently -H, -C1~C6 alkyl, -C1~C3 haloalkyl, aryl, and -C(O)N(R) a )(R b ), -C(O)R c , -CO2R c , -SO2N(R a )(R b ), or -SOR c And each R a and R b These are independently H or C1-C6 alkyl groups. Each W is independently a bond, an alkylene group, an arylene group, or a heteroarylene group, such as -O-arylene- or -(CH2) a-Arirene-, -SO2-Arirene-, -NH-Arirene-, -S-Arirene-, -O-Heteroarirene-, -(CH2) a -heteroarylene-, -SO2-heteroarylene-, -NH-heteroarylene-, -S-heteroarylene-, -(-O-(CH2) a -) x -,-(-NH-(CH2) a -) x -,-(-S-(CH2) a -) x -, [ka] There, a is between 0 and 100, x is between 1 and 100, and each arylene or heteroarylene moiety may be substituted or unsubstituted. Each Z is either a cationic or anionic moiety. Each L independently has -O-, -S-, -N-, C1~C6 substituted or unsubstituted alkyl groups. Ren, C1~C3 Haroalkiren, [ka] A connecting part selected from the group consisting of, A' is a covalent bond to A, Z' is a covalent bond to Z, *teeth, [ka] It is a covalent bond to, [ka] These are binding sites to multiple cyclodextrin carbon atoms, x ranges from 0 to 8. y1 is 1 to 4, y2 is between 1 and 4. y3 is between 0 and 4.

[0039] Each Z is a cationic moiety or an anionic moiety. For example, in some embodiments, each Z is a cationic moiety. In certain embodiments, each cationic moiety is independently —N(R 3 )3 + , —P(R 3 )3 + , —S(R 3 )2 + , or —heteroaryl + , and each R 3 is independently —H, —C1-C6 alkyl, —C1-C3 haloalkyl, —aryl, —C(O)N(R a )(R b ), —C(O)R c , —CO2R c , —SO2N(R a )(R b ), or —SOR c , and each R a and R b are independently H, or C1-C6 alkyl. For example, in some embodiments, each cationic moiety is —N(R 3 )3 + , and each R 3 is H, or C1-C6 alkyl. Thus, in some embodiments, each cationic moiety is —N(Me)3 + or —NH3 + . In some embodiments, each cationic moiety is —N(Me)3 + . In some embodiments, each cationic moiety is independently —heteroaryl + . In the context of the present disclosure, various charged heteroaryls are contemplated and will be readily apparent to those skilled in the art. For example, in some embodiments, —heteroaryl + may refer to pyridinium, pyrrolidinium, imidazolium, triazolium, tetrazolium, etc. In some embodiments, each Z is an anionic moiety. In certain embodiments, each anionic moiety is

Chemical formula

[0040] According to certain embodiments of the present disclosure, each W is independently a bond, an alkylene group (e.g., C1-C 10 , C 10 -C 20 , or C 20 -C 100 ), an arylene group, a heteroarylene group, -O-arylene-, -(CH2) a -arylene-, -SO2-arylene-, -NH-arylene-, -S-arylene-, -O-heteroarylene-, -(CH2) a -heteroarylene-, -SO2-heteroarylene-, -NH-heteroarylene-, -S-heteroarylene-, -(-O-(CH2) a -) x -, -(-NH-(CH2) a -) x -, or -(-S-(CH2) a -) x- where a is between 0 and 100, and x is between 1 and 100, and each arylene or heteroarylene moiety may be substituted or unsubstituted. The term "arylene" refers to a divalent group derived from an aryl group (including phenyl, biphenyl, naphthyl, etc. as described herein) by removing hydrogen atoms from two ring carbons. For example, an arylene may contain phenyl, where the two valence electrons are located in ortho, meta, or para orientations. In the case of polycyclic arylenes, the two valence electrons may be on the same ring or different rings. Arylenes can be derived from any aromatic ring as described herein and may be substituted or unsubstituted. Similarly, the term "heteroarylene" refers to a divalent group derived from a heteroaryl group (including furyl, pyridyl, etc. as described herein) by removing hydrogen atoms from two ring atoms (which may be carbon or heteroatoms). The valence electrons may be on the same ring or different rings (in the case of polycyclic heteroaromatic rings) and may be on any two ring atoms. Heteroarylenes can be derived from any heteroaromatic ring described herein and may be substituted or unsubstituted. Therefore, in some embodiments, each W is a bond (i.e., a covalent bond). In other embodiments, each W is an alkylene group. For example, each W may be methylene (-CH2-), ethylene (-CH2CH2-), propylene (-CH2CH2CH2-), isopropylene (-CH(CH3)CH2-), n-butylene (-CH2CH2CH2CH2-), sec-butylene (-CH2(CH2CH3)CH2-), etc. In some embodiments, each W is methylene (-CH2-). In some embodiments, each W is an arylene group (phenylene). In some embodiments, each W is a heteroarylene group (furyl, pyridyl). In some embodiments, each W is -O-arylene-(-O-phenylene). In some embodiments, each W is -(CH2) a-Arylene-(-CH2-phenylene). In some embodiments, each W is -SO2-arylene-(-SO2-phenylene). In some embodiments, each W is -NH-arylene-(-NH-phenylene). In some embodiments, each W is -S-arylene-(-S-phenylene). In some embodiments, each W is a heteroarylene group (frylene, pyridylene). In some embodiments, each W is -O-heteroarylene-(-O-pyridinylene). In some embodiments, each W is -(CH2) a -heteroarylene-(-CH2-pyridinylene). In some embodiments, each W is -SO2-heteroarylene-(-SO2-pyridinylene). In some embodiments, each W is -NH-heteroarylene-(-NH-pyridinylene). In some embodiments, each W is -S-heteroarylene-(-S-pyridinylene). In some embodiments, W is -(O-CH2-CH2) x - is. In some embodiments, W is -O-CH2-CH2-. In some embodiments, W is [ka] And, where A' is a covalent bond to A and Z' is a covalent bond to Z. In some embodiments, W is [ka] That is the case.

[0041] In some embodiments, each of -WZ combines to form -O-CH2-CH2-N(R)3 + In some embodiments, each of -WZ combines to form -O-CH2-CH2-N(Me)3 + Forms. In some embodiments, each of -WZ together [ka] It forms.

[0042] In some embodiments, each L is a connecting portion. In some embodiments, each L is independently -O-, -S-, -N-, [ka] A connected part selected from the group consisting of, where A' is a covalent bond to A, and * is, [ka] It is a covalent bond to (representing bonding sites to multiple cyclodextrin carbon atoms as described herein). In some embodiments, each L is independently -O-. In certain embodiments, L is independently [ka] Or, if -O-, the oxygen atom may be glycosyl oxygen from multiple cyclodextrins of the porous polymer material of the present disclosure. For example, in some embodiments, if each L is independently -O-, the oxygen atom is glycosyl oxygen from multiple cyclodextrin atoms of the porous polymer material of the present disclosure.

[0043] In some embodiments, A is an aryl or heteroaryl moiety. In some embodiments, A is an aryl moiety. For example, A may be phenyl, biphenyl, naphthyl, anthracenyl, phenalenyl, phenantrenyl, indanyl, indenyl, tetrahydronaphthalenyl, or tetrahydrobenzoanurenyl. In some embodiments, A is a heteroaryl moiety. For example, A may be benzothiophene, furyl, thienyl, pyrrolyl, pyridyl, pyrazinyl, pyrazolyl, pyridadinyl, pyrimidinyl, imidazolyl, isoxazolyl, oxazolyl, oxadiazolyl, pyrazinyl, indolyl, thiophen-2-yl, quinolyl, benzopyranil, isothiazolyl, thiazolyl, thiadiazolyl, thieno[3,2-b]thiophene, triazolyl, triazinyl Lu, imidazo[1,2-b]pyrazolyl, flo[2,3-c]pyridinyl, imidazo[1,2-a]pyridinyl, indazolyl, pyrrolo[2,3-c]pyridinyl, pyrrolo[3,2-c]pyridinyl, pyrazolo[3,4-c]pyridinyl, benzimidazolyl, thieno[3,2-c]pyridinyl, thieno[2,3-c]pyridinyl, thieno[2,3-b]pyridinyl, benzothiazolyl, indolyl Indolinyl, indolinonyl, dihydrobenzothiophenyl, dihydrobenzofuranyl, benzofuran, chromanil, thiochromanil, tetrahydroquinolinyl, dihydrobenzothiazine, dihydrobenzooxanil, quinolinyl, isoquinolinyl, 1,6-naphthilidinyl, benzo[de]isoquinolinyl, pyrido[4,3-b][1,6]naphthilidinyl, thieno[2,3-b]pyrazine Lu, quinazolinyl, tetrazolo[1,5-a]pyridinyl, [1,2,4]triazolo[4,3-a]pyridinyl, isoindolyl, pyrrolo[2,3-b]pyridinyl, pyrrolo[3,4-b]pyridinyl, pyrrolo[3,2-b]pyridinyl, imidazo[5,4-b]pyridinyl, pyrrolo[1,2-a]pyridinyl, tetrahydropyrrolo[1,2-a]pyridinyl, 3,4-dihydro-2H-1λ 2-Pyrrolo[2,1-b]pyrimidine, dibenzo[b,d]thiophene, pyridine-2-one, flo[3,2-c]pyridinyl, flo[2,3-c]pyridinyl, 1H-pyrido[3,4-b][1,4]thiadinyl, benzoxazolyl, benzoisoxazolyl, flo[2,3-b]pyridinyl, benzothiophenyl, 1,5-naphthilidinyl, flo[3,2-b]pyridine, [1,2,4]triazolo[1,5-a]pyridinyl, benzo[1,2,3]triazolyl, imidazo[1,2-a]pyrimidinyl, [1,2,4 This could be triazolo[4,3-b]pyridazinyl, benzo[c][1,2,5]thiadiazolyl, benzo[c][1,2,5]oxadiazole, 1,3-dihydro-2H-benzo[d]imidazole-2-one, 3,4-dihydro-2H-pyrazolo[1,5-b][1,2]oxazinyl, 4,5,6,7-tetrahydropyrazolo[1,5-a]pyridinyl, thiazolo[5,4-d]thiazolyl, imidazo[2,1-b][1,3,4]thiadiazolyl, thieno[2,3-b]pyrrolyl, or 3H-indolyl. In some embodiments, A is selected from the group consisting of phenyl, naphthyl, pyridyl, benzofuranyl, pyrazinyl, pyridadinyl, pyrimidinyl, triazinyl, quinoline, benzoxazole, benzothiazole, 1H-benzimidazole, isoquinoline, quinazoline, quinoxaline, pyrrole, indole, biphenyl, pyrenyl, and anthracenyl. In some embodiments, A is phenyl In some embodiments, A is an aryl or heteroaryl ring system as described in U.S. Patent No. 9,855,545, which is incorporated herein by reference in its entirety.

[0044] In some embodiments, A is a polymerization product of a commercially available diisocyanate. For example, in some embodiments, A is a polymerization product of commercially available aryl diisocyanates, including but not limited to 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-methylenediphenyl diisocyanate, 2,4'-methylenediphenyl diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(1-isocyanato-1-methylethyl)benzene, 3,3'-dichloro-4,4'-diisocyanato-1,1'-biphenyl, 3,3'-dimethyl-4,4'-biphenylenediisocyanate, 4,4'-oxybis(phenylisocyanate), 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, 4-chloro-6-methyl-1,3-phenylenediisocyanate, and 1-chloromethyl-2,4-diisocyanatobenzene. In some embodiments, A is, [ka] Hereinafter, the dashed line indicates any substituent bonded to A as defined herein. In some embodiments, A is [ka] Hereinafter, the dashed line indicates any substituent bonded to A as defined herein. In some embodiments, A is [ka] The dashed line indicates any substituent bonded to A as defined herein, and the -Me, -Cl, and -CH2-Cl groups bonded to the aryl ring of the above structure are R 1 The -CH2- and -C(Me)2- groups, which correspond to the group and are bonded to the aryl ring, correspond to the L group. In some embodiments, A is [ka] The dashed line indicates any substituent bonded to A as defined herein, and the -Me and -Cl groups bonded to the aryl ring of the above structure are R 1 It corresponds to the base.

[0045] The porous polymer material of this disclosure comprises a plurality of cyclodextrins having a plurality of crosslinks having formula (I). The plurality of cyclodextrins of this disclosure may be any cyclodextrins containing 6 to 12 glucose units. For example, in some embodiments, the plurality of cyclodextrins of this disclosure are selected from the group consisting of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and combinations thereof. In some embodiments, each cyclodextrin is a β-cyclodextrin.

[0046] Multiple bridges having formula (I) 1 The base is each R 1 These are H, C1-C6 alkyl, C1-C3 haloalkyl, aryl, heteroaryl, -CF3, -SO3H, -CN, -NO2, -NH2, -NCO, -C(O)2R 3 ,-C(O)N(R 3 )2, and -halogens are independently selected. In a particular embodiment, each R 1 These are H, C1-C6 alkyl, C1-C3 haloalkyl, aryl, heteroaryl, -CF3, -SO3H, -CN, -NO2, -NH2, -NCO, -C(O)2R 3 ,-C(O)N(R 3 )2, and -halogens are independently selected from the group. In a particular embodiment, 0 to 8 R on a plurality of bridges having formula (I) 1 There are bases. For example, 0, 1, 2, 3, 4, 5, 6, 7, or 8 R 1 The base exists in each of the individual bridges having formula (I). 1 , R 2It is understood that any position of A that is not substituted with -WZ or -L- is either unsubstituted or has one or more H atoms necessary to satisfy the valence at that position. As will be recognized by those skilled in the art, each R of each bridge in formula (I) 1 The number of groups may vary throughout the porous polymer material of this disclosure. For example, R 1 If the polymerized porous material of the present invention is -F, and is exposed to a reactant that can perform substitution (e.g., choline chloride), some -F groups on the crosslinks may be substituted, but in other crosslinks, the -F groups may not react because they are effectively protected from the reactant. Therefore, the porous polymer material of the present disclosure may have multiple linking groups of formula (I), and each individual linking group may independently have 0 to 8 (e.g., 1, 2, or 3) R groups. 1 It can have a base.

[0047] In some embodiments, the porous polymer material of the present disclosure has, on average, R, expressed as a decimal number. 1 , R 2 It can be characterized as having a -WZ or -L- group in each crosslinking group. The decimal number of these substituents can be calculated by dividing the total number of such groups by the total number of crosslinks in the porous polymer material. For example, half of the crosslinking groups are -O-CH2-CH2-N(Me)3 + When functionalized with a group (for example, if W is -O-CH2-CH2- and Z is -N(Me)3), the corresponding -O-CH2-CH2-N(Me)3 for each crosslinking group is -WZ. + The average number (or decimal) of the base is 0.5. 1For such base decimals, approximately 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, Approximately 2.5, approximately 2.5, approximately 2.7, approximately 2.8, approximately 2.9, approximately 3.0, approximately 3.1, approximately 3.2, approximately 3.3, approximately 3.4, approximately 3.5, approximately 3.6, approximately 3.7, approximately 3.8, approximately 3.9, approximately 4.0, approximately 4.1, approximately 4.2, approximately 4.3, approximately 4.4, approximately 4.5, approximately 4.6, approximately 4.7, approximately 4.8, approximately 4.9, approximately 5.0, approximately 5.1, approximately 5.2, approximately Includes values ​​of 5.3, approximately 5.4, approximately 5.5, approximately 5.6, approximately 5.7, approximately 5.8, approximately 5.9, approximately 6.0, approximately 6.1, approximately 6.2, approximately 6.3, approximately 6.4, approximately 6.5, approximately 6.6, approximately 6.7, approximately 6.8, approximately 6.9, approximately 7.0, approximately 7.1, approximately 7.2, approximately 7.3, approximately 7.4, approximately 7.5, approximately 7.6, approximately 7.7, approximately 7.8, approximately 7.9, or approximately 8.0, and includes all ranges between any of these values. 2For such a base decimal includes approximately 0, approximately 0.1, approximately 0.2, approximately 0.3, approximately 0.4, approximately 0.5, approximately 0.6, approximately 0.7, approximately 0.8, approximately 0.9, approximately 1.0, approximately 1.1, approximately 1.2, approximately 1.3, approximately 1.4, approximately 1.5, approximately 1.6, approximately 1.7, approximately 1.8, approximately 1.9, approximately 2.0, approximately 2.1, approximately 2.2, approximately 2.3, approximately 2.4, approximately 2.5, approximately 2.5, approximately 2.7, approximately 2.8, approximately 2.9, approximately 3.0, approximately 3.1, approximately 3.2, approximately 3.3, approximately 3.4, approximately 3.5, approximately 3.6, approximately 3.7, approximately 3.8, approximately 3.9, or approximately 4.0, and includes all ranges between any of these values. For -WZ, such base decimals include approximately 1.0, approximately 1.1, approximately 1.2, approximately 1.3, approximately 1.4, approximately 1.5, approximately 1.6, approximately 1.7, approximately 1.8, approximately 1.9, approximately 2.0, approximately 2.1, approximately 2.2, approximately 2.3, approximately 2.4, approximately 2.5, approximately 2.5, approximately 2.7, approximately 2.8, approximately 2.9, approximately 3.0, approximately 3.1, approximately 3.2, approximately 3.3, approximately 3.4, approximately 3.5, approximately 3.6, approximately 3.7, approximately 3.8, approximately 3.9, or approximately 4.0, and include all ranges between any of these values. For -L-, such base decimals include approximately 1.0, approximately 1.1, approximately 1.2, approximately 1.3, approximately 1.4, approximately 1.5, approximately 1.6, approximately 1.7, approximately 1.8, approximately 1.9, approximately 2.0, approximately 2.1, approximately 2.2, approximately 2.3, approximately 2.4, approximately 2.5, approximately 2.5, approximately 2.7, approximately 2.8, approximately 2.9, approximately 3.0, approximately 3.1, approximately 3.2, approximately 3.3, approximately 3.4, approximately 3.5, approximately 3.6, approximately 3.7, approximately 3.8, approximately 3.9, or approximately 4.0, and include all ranges between any of these values.

[0048] Each R 2 R is independently H, -OH, -O-metal cation, alkyl, aryl, heteroaryl, -SH, -S-metal cation, -S-alkyl, -C(O)2H, or -C(O)NH2. In some embodiments, each R 2 is H. In some embodiments, each R 2 is -OH. In some embodiments, each R 2 is a -O-metal cation. In some embodiments, each R 2 is alkyl. In some embodiments, each R 2R is an aryl (e.g., substituted or unsubstituted phenyl or naphthyl). In some embodiments, each R 2 R is a heteroaryl (for example, a substituted or unsubstituted 5-membered or 6-membered heteroaryl ring having one, two, or three ring heteroatoms selected from the group consisting of O, S, or N). In some embodiments, each R 2 is -SH. In some embodiments, each R 2 is a -S-metal cation. In some embodiments, each R 2 is an -S-alkyl group. According to embodiments of this disclosure, one, two, three, or four R groups are used. 2 There may be 0, 1, 2, 3, or 4 R elements. 2 The group is present on multiple bridges having formula (I). As will be recognized by those skilled in the art, each of the multiple linking groups having formula (I) 2 The number of R groups may vary for each individual linking group throughout the porous polymer material of the present disclosure. Thus, the porous polymer material of the present disclosure may contain multiple linking groups of formula (I), each individual linking group independently having, for example, 0, 1, 2, 3, or 4 R groups. 2 It may have one or more R groups. 2 If the group is located on a linked group of multiple formulas (I), each R 2 The bases may be the same or different. For example, in some embodiments, one or more R 2 The group is an -O-metal cation, and one or more R 2 The group is -OH.

[0049] Each R 3 These are independently -H, -C1~C6 alkyl, -C1~C3 haloalkyl, aryl, and -C(O)N(R) a )(R b ), -C(O)R c , -CO2R c , -SO2N(R a )(R b ), or -SOR c And each R a and R bR is independently H or C1-C6 alkyl. In some embodiments, each R 3 is Me. In some embodiments, each R 3 H is R 3 If the compound is an aryl compound, the aryl compound may be, for example, a substituted or unsubstituted phenyl or naphthyl compound.

[0050] In certain embodiments, x is 1 to 4. For example, x may be 1, 2, 3, or 4. In some embodiments, x is 1 or 2, and R 1 It is -F.

[0051] In certain embodiments, y1 is 1 to 4. For example, y1 may be 1, 2, 3, or 4. In some embodiments, y1 is 1 to 2.

[0052] In a particular embodiment, y2 is either 1 or 2.

[0053] In a particular embodiment, y3 is 0 or 1.

[0054] In a particular embodiment, the porous polymer material of the present disclosure is of formula (II): [ka] It contains multiple cyclodextrins crosslinked by multiple crosslinks having, During the ceremony, y2 is either 1 or 2. x is either 1 or 2. In some embodiments, y2 is 2 and x is 1. In some embodiments, each cyclodextrin is β-cyclodextrin.

[0055] In a particular embodiment, the porous polymer material of the present disclosure is a material of formula (III): [ka] Includes multiple linkers,

[0056] In the formula, one R 4 is -H and one R 4 is -Me. In some embodiments, each cyclodextrin is β-cyclodextrin.

[0057] In various embodiments, the porous polymer materials of the Disclosure are prepared by crosslinking cyclodextrins of the same structure with crosslinking agents of the same structure. In some embodiments, the porous polymer materials of the Disclosure are prepared by crosslinking cyclodextrins of the same structure with two, three, four, or more different crosslinking agents. In various embodiments, the porous polymer materials of the Disclosure are prepared by crosslinking two, three, or four different cyclodextrins (i.e., having different structures) with crosslinking agents of the same structure. In some embodiments, the porous polymer materials of the Disclosure are prepared by crosslinking two, three, or four different cyclodextrins with two, three, four, or more It is prepared by crosslinking with different crosslinking agents.

[0058] In some embodiments, some of the crosslinks in the porous polymer material do not contain a cationic or anionic moiety (i.e., the group "Z" in formula (I)). In such embodiments, the porous polymer material comprises multiple crosslinkers of formula (I) and multiple crosslinkers having a structure similar to the crosslinkers of formula (I), except that they lack a cationic or anionic moiety corresponding to the group "Z". Thus, for example, such crosslinkers lacking a cationic or anionic moiety may have any of the crosslinker structures described in U.S. Patent No. 10,086,360, which is incorporated herein by reference for any purpose, for example, structure (a) below: [ka] Or the structure below (b): [ka] Alternatively, the material may include multiple crosslinking agents in combination of structures (a) and (b) (where x in structure (b) is 0, 1, 2, 3, or 4). In such embodiments of porous polymer materials having crosslinking agents of structure (a) and / or structure (b), such materials may also include charged crosslinking agents of formula (I) as described herein.

[0059] In further embodiments, the porous polymer material of the present disclosure has the following structure (c): [ka] (In the formula, X - Cl - It contains multiple cationic crosslinking agents (such as pharmaceutically acceptable anionic counterions).

[0060] In yet another embodiment, the porous polymer material of the present disclosure has the following structure (d): [ka] (In structure (d), x is 0, 1, 2, 3, or 4, X - is Cl - It contains multiple cationic crosslinking agents (such as pharmaceutically acceptable anionic counterions).

[0061] In further embodiments, the porous polymer material of the Disclosure comprises a plurality of cationic crosslinkers of structure (c) and a plurality of cationic crosslinkers of structure (d). Any crosslinker of the Disclosure having an aromatic halide group can be modified to provide a charged moiety by reacting with choline chloride under suitable conditions, for example, as described herein.

[0062] In other embodiments, the porous polymer material of the present disclosure has the following structure (e): [ka] It contains multiple anionic crosslinking agents.

[0063] Alternatively, the cationic counterion (Na) of structure (e) + (shown as H) + or K + This may include any other pharmaceutically acceptable cationic counterion, such as (but not limited to) these.

[0064] In yet another embodiment, the porous polymer material of the present disclosure has the following structure (f): [ka] The material comprises multiple anionic crosslinking agents (where x in structure (f) is 0, 1, 2, 3, or 4).

[0065] In yet another embodiment, the porous polymer material of the present disclosure has multiple structures (e) The material includes a thionic crosslinking agent and multiple cationic crosslinking agents of structure (f).

[0066] In some embodiments, the disclosure provides a porous polymer material comprising a plurality of cyclodextrin moieties crosslinked by one or more polyisocyanates. In some embodiments, the plurality of cyclodextrins are β-cyclodextrins. In some embodiments, one or more polyisocyanates are aryl diisocyanates, including but not limited to 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-methylenediphenyl diisocyanate, 2,4'-methylenediphenyl diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(1-isocyanato-1-methylethyl)benzene, 3,3'-dichloro-4,4'-diisocyanato-1,1'-biphenyl, 3,3'-dimethyl-4,4'-biphenylenediisocyanate, 4,4'-oxybis(phenylisocyanate), 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, 4-chloro-6-methyl-1,3-phenylenediisocyanate, and 1-chloromethyl-2,4-diisocyanatobenzene, as well as combinations thereof. In some embodiments, the aryl diisocyanate is 2,4-toluene diisocyanate. In some embodiments, one or more polyisocyanates are aliphatic diisocyanates including, but not limited to, 4,4'-diisocyanate-methylenedicyclohexane (HMDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), L-lysine diisocyanate (LDI), trimethylhexamethylene diisocyanate (TMDI), 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-diisocyanatobutane, trimethyl-1,6-diisocyanatohexane, 1,6-diisocyanato-2,2,4-trimethylhexane, trans-1,4-cyclohexylene diisocyanate, 1,8-diisocyanatooctane, 1,12-diisocyanatotododecane, and combinations thereof. In some embodiments, the multiple cyclodextrins are β-cyclodextrins, and one or more polyisocyanates are 2,4-toluenediisocyanates. In some embodiments, the porous polymer material is about 10 m.2 / g~2000m 2 It has a Brunauer-Emmett Teller (BET) surface area of ​​about 10 m² / g. For example, in some embodiments, the porous polymer material has about 10 m² / g. 2 / g, 20m 2 / g, 30m 2 / g, 40m 2 / g, 50m 2 / g, 75m 2 / g, 100m 2 / g, 150m 2 / g, 200m 2 / g, 250m 2 / g, 300m 2 / g, 350m 2 / g, 400m 2 / g, 450m 2 / g, 500m 2 / g, 550m 2 / g, 600m 2 / g, 650m 2 / g, 700m 2 / g, 750m 2 / g, 800m 2 / g, 850m 2 / g, 900m 2 / g, 950m 2 / g, 1000m 2 / g, 1050m 2 / g, 1100m 2 / g, 1150m 2 / g, 1200m 2 / g, 1250m 2 / g, 1300m 2 / g, 1350m 2 / g, 1400m 2 / g, 1450m 2 / g, 1500m 2 / g, 1550m 2 / g, 1600m 2 / g, 1650m 2 / g, 1700m 2 / g, 1750m 2 / g, 1800m 2 / g, 1850m 2 / g, 1900m 2 / g, 1950m 2 / g~about 2000m2 It has a BET surface area of ​​0 mmol / g, encompassing all integers and ranges between these values. In some embodiments, the porous polymer material has an amine content of about 0 mmol / g to about 1.0 mmol / g. In some embodiments, the porous polymer material has an amine content of about 0.1 mmol / g to about 1.0 mmol / g. In some embodiments, the porous polymer material has an amine content of about 0.15 mmol / g to about 0.35 mmol / g. For example, in some embodiments, the amine content is about 0.15 mmol / g, about 0.16 mmol / g, about 0.17 mmol / g, about 0.18 mmol / g, about 0.19 mmol / g, about 0.20 mmol / g, about 0.21 mmol / g, about 0.22 mmol / g, about 0.23 mmol / g, about 0.24 mmol / g, about 0.25 mmol / g, about 0.26 mmol / g, about 0.27 mmol / g, about 0.28 mmol / g, about 0.29 mmol / g, about 0.30 mmol / g, about 0.31 mmol / g, about 0.32 mmol / g, about 0.33 mmol / g, about 0.34 mmol / g, And may be approximately 0.35 mmol / g, encompassing all ranges between these values. Although not bound by any particular theory, it has been found that using as-is CD (i.e., undried) in polymer synthesis results in polymers having a higher amine content than similar polymers described in the prior art, leading to a higher affinity for certain trace contaminants such as PFAS.

[0067] In certain embodiments, the molar ratio of cyclodextrin to the linking group of formula (I), (II), or (III) is in the range of about 1:1 to about 1:X, where X is three times the average number of glucose subunits in the cyclodextrin. In certain embodiments, the molar ratio of cyclodextrin to the linking group of formula (I), (II), or (III) is about 1:6. In certain embodiments, the molar ratio of cyclodextrin to the linking group of formula (I), (II), or (III) is about 1:5. In certain embodiments, the molar ratio of cyclodextrin to the linking group of formula (I), (II), or (III) is about 1:4. In certain embodiments, the molar ratio of cyclodextrin to the linking group of formula (I), (II), or (III) is about 1:3. In certain embodiments, the molar ratio of cyclodextrin to the linking group of formula (I), (II), or (III) is about 1:2. In various embodiments, the molar ratio of the cyclodextrin portion to the aryl crosslinked portion is approximately 1:1 to approximately 1:24, including approximately 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, 1:10, 1:10.5, 1:11, 1:11.5, and 1:1. 2, including approximately 1:12.5, approximately 1:13, approximately 1:13.5, approximately 1:14, approximately 1:14.5, approximately 1:15, approximately 1:15.5, approximately 1:16, approximately 1:16.5, approximately 1:17, approximately 1:17.5, approximately 1:18, approximately 1:18.5, approximately 1:19, approximately 1:19.5, approximately 1:20, approximately 1:20.5, approximately 1:21, approximately 1:21.5, approximately 1:22, approximately 1:22.5, approximately 1:23, approximately 1:23.5, or approximately 1:24, and including all ratio ranges between these values. In one embodiment, the molar ratio of the cyclodextrin portion to the aryl crosslinked portion is approximately 1:2.5 to approximately 1:10.

[0068] In some embodiments, compositions according to the Disclosure comprise one or more porous polymer materials of the Disclosure and one or more support materials, wherein the porous polymer materials are bonded to the support materials (e.g., covalently, adhesively, or mechanically, as described herein). For example, in some embodiments, a composition comprises a porous polymer material comprising a plurality of cyclodextrins crosslinked by a plurality of crosslinks having formulas (I), and / or (II), and / or (III). Examples of support materials include cellulose (e.g., cellulose fibers), carbon-based materials such as activated carbon, graphene oxide, and carbon oxide materials, silica, alumina, natural or synthetic polymers, and natural or synthetic polymers modified to include surface hydroxyl groups. Those skilled in the art will recognize any material that has suitable mechanical or other properties to function as a support and can be covalently bonded to the porous polymer material, or can function as a suitable support material when the porous polymer material is adhesively bonded to the support by a suitable binder material. In one embodiment, the composition is in the form of a membrane or column packing material. In one embodiment, the support is a fiber (e.g., cellulose, nylon, polyolefin, or polyester fiber). In one embodiment, the support is a porous particulate material (e.g., porous silica and porous alumina). In one embodiment, the support is a woven or nonwoven fabric. In one embodiment, the support is clothing (such as protective clothing), or a surgical or medical drape, covering, or sanitary product.

[0069] In some embodiments, P-CDP can be grafted or bonded (e.g., chemically or mechanically) onto a support to provide an adsorbent with particle size and morphology that is well controlled to give ideal flow properties. The term refers to a bond formed between two materials by pressure, ultrasonic bonding, and / or other mechanical bonding processes that do not involve the application of intentional heat, such as mechanical confounding. The physical confounding and coating of microfibrils to hold micron-sized particulate matter in place is a typical example of mechanical bonding. The term mechanical bonding does not include bonds formed using adhesives or chemical grafting. In some embodiments, P-CDP can provide adsorbents whose particle size and morphology have been further manipulated (e.g., by granulation or milling) so that particles with well-controlled particle size and morphology are provided to give ideal flow properties when grafted or bonded (e.g., chemically or mechanically) onto a support.

[0070] P-CDP support complexes can be prepared by a variety of methods, including conventional grafting methods. As used herein, the term “grafting” refers to covalently bonding P-CDP to a substrate surface by a coupling reaction between one or more functional groups on P-CDP and one or more functional groups on a substrate. In some embodiments, grafting includes an “in situ” process as described herein, in which a cyclodextrin, a linking group of the disclosure, and a substrate having a surface-bound nucleophile (e.g., hydroxyl) react with each other, and the linking group of the disclosure reacts with the hydroxyl group of the cyclodextrin and the surface nucleophile of the substrate to form P-CDP partially bonded to the substrate via one or more linking groups of the disclosure. Substrates having surface-bound nucleophiles include, but are not limited to, hydroxyl (e.g., microcrystalline cellulose), amines, phosphines, and thiols.

[0071] In some embodiments, the “grafted” P-CDP support complex is prepared by first synthesizing P-CDP in a dedicated chemical reactor that provides appropriate control over reaction conditions and material purification for producing optimized P-CDP particles. The P-CDP is then chemically reacted with a suitably functionalized substrate. For example, a substrate functionalized with a carboxylic acid group (or its activated form, such as an acid halide or anhydride known in the art) can react with one or more hydroxyls on the P-CDP to form an ester bond with the substrate. Alternatively, the P-CDP may be suitably functionalized by subsequent modification of the P-CDP (e.g., by the selection of functionalized cyclodextrins described herein) so that it can react with suitable functional groups on the substrate. Any suitable reaction chemistry can be attempted, such as the reaction of carboxylic acids (and their derivatives) to hydroxyl groups to form ester bonds, the reaction of carboxylic acids (and their derivatives) to amine groups to form amide bonds, the reaction of isocyanates to alcohols to produce urethanes, the reaction of isocyanates to amines to produce urea, the reaction of cyclic carbonates to amines to produce urethanes, the reaction of thiols to alkenes or alkynes to produce thioethers, the reaction of epoxides to amine groups, and photochemical reactions of olefins with acrylates, methacrylates, thiols, etc. The reactive functional groups described herein may be present on either the P-CDP or the substrate, provided that the reaction forms a covalent bond between the substrate and the P-CDP. For example, in the case of the reactive functional groups of hydroxyl and carboxylic acids (which form ester bonds after the reaction), the hydroxyl group may be present on the P-CDP and the carboxyl group may be present on the substrate (or vice versa).

[0072] In other embodiments, the substrate can be coated with a "primer" having the reactive functional groups described above. The primer adheres to the surface of the substrate and reacts with appropriately functionalized P-CDP under appropriate conditions to form a covalent bond between the P-CDP and the primer.

[0073] P-CDP particles can be manipulated to obtain a specific particle size. In some embodiments, P-CDP is produced in the form of crosslinked particles that may require further particle size reduction. This is done (for example, to form a stable dispersion or slurry, or to provide optimal flow properties). Various means, such as grinding or milling, which are immediately apparent to those skilled in the art, can be used to reduce the particle size of P-CDP. Using grinding and milling, small particles of less than 1 micron in size can be produced. Common milling operations can be used by those skilled in the art, and both wet and dry milling are available. Milling can be used in a variety of ways, including but not limited to ball mills, self-sharpening mills, SAG mills, pebble mills, rod mills, barstone mills, tower mills, vertical shaft impactor mills, etc. Milling media include, but are not limited to, metals, silicates, and other inorganic materials in various form factors, including rods, balls, and irregular shapes. In some embodiments, milling is performed on a dry P-CDP powder material in a drying process to produce a finer dry powder, or on a wet aqueous slurry of P-CDP powder with or without emulsifiers to produce a finer particulate dispersion. Emulsifiers can be used that include, but are not limited to, small molecule and polymer surfactant compounds having nonionic, anionic, or cationic properties, which will be immediately apparent to those skilled in the art. Those skilled in the art will recognize that using a fine particulate form factor offers various advantages, including: (1) a more stable aqueous dispersion that remains uniform over time due to its resistance to separation; (2) enabling high weight loadings of 50% or more of the material in the dispersion; (3) producing particulate matter that can be uniformly coated or applied to various substrates, surfaces, fibers, threads, fabrics, etc., resulting in a finished material that produces minimally perceptible changes to the "hand"; and (4) producing a dispersion that is stable against dilution and mixing with other emulsions or solutions such as binders, surfactants, wetting agents, or softeners. In some embodiments, the final particle diameter includes ranges of less than 1 micron, 1 to 5 microns, 5 to 10 microns, 10 to 15 microns, 15 to 20 microns, or in between.

[0074] If larger particle sizes are desired, the composition can be granulated to form aggregates of larger particle sizes. Therefore, in some embodiments, granules (e.g., self-supporting granules) are produced from P-CDP particle powder of various sizes. Generally, this process converts P-CDP particle powder in size forms ranging from 1 to 30 microns into granules of 100 microns, 200 microns, 300 microns, and larger. This process can be carried out by granulation techniques common in the pharmaceutical industry (Handbook of Granulation Technology, Ed. Parikh, DM, 2005, Taylor & Francis Group), where powders are bonded to each other in batch or continuous mode by physical and / or chemical means. In its simplest form, P-CDP particles are mechanically blended with a fluid (e.g., aqueous) mixture containing an adhesive binder (usually synthetic, semi-synthetic, or natural polymer). Suitable semi-synthetic polymers available include cellulose ethers, specifically ethylcellulose, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, starch, and starch derivatives. Suitable fully synthetic polymers such as polyvinylpyrrolidone or polyethylene glycol can be used. Other suitable binders include polyamidoamine epichlorohydrin (PAE) or polymeric glyoxal crosslinkers, polyvinyl alcohol, and starch-based sizing and other coatings used in the textile and paper industries. To produce durable granules that are poorly soluble in water or other solvents, further covalent crosslinking can be promoted by adding small molecule crosslinkers such as glyoxal, formaldehyde, diisocyanate, and / or diepoxide functional groups. In addition to covalent crosslinking, electrostatic aggregation of polyelectrolytes can also be used as a binding motif, forming suitable adhesive properties when cationic polyelectrolytes are blended with anionic polyelectrolytes in the presence of P-CDP powder and / or supporting structures. Polycations commonly used for aggregation include, but are not limited to, polydiallyldimethylammonium chloride (polyDADMAC), acidic polyethyleneimine, and polyacrylamide. Polyanions may include, but are not limited to, sodium polyacrylate, sodium polystyrene sulfonate, and polyvinyl sulfonate, which are commonly used for aggregation.

[0075] Mechanical mixing during granulation can be carried out by low-shear processes such as rotary drum mixing or overhead mechanical stirring. As will be immediately apparent to those skilled in the art, the stirring speed and the overall length of stirring time affect the granule size. Granulation can also be carried out in a fluidized bed or by spray drying technology. In either case, the P-CDP particles are combined with an aqueous or solvent-based mixture containing a binder compound, and mechanical or physical stirring is performed at a specified shear force for a predetermined number of cycles. The resulting particles may exhibit a stepwise growth change in the average particle diameter and also a change in polydispersity. The physical properties of these granules depend on the selected binder, crosslinking chemistry, and the physical process used for granulation. These larger granular particles are suitable for packed-bed column filtration, which is commonly used for water filtration and industrial separation.

[0076] In some embodiments, the Disclosure provides a stable aqueous dispersion containing P-CDP particles. In some embodiments, the P-CDP particles of the Disclosure that can be used in such a stable aqueous dispersion are about 1 μm to about 150 μm in size. For example, the P-CDP particles are about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84 ,85,86,87,88,89,90,91,92,93,94,95,96,97,98,99,100,101,102,103,104,105,106,107,108,109,110,111,112,113,114,115,116,117,118,119,12 The particle sizes are 0, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, and approximately 150 μm. Stable aqueous dispersions can be used in "grafting" applications. For example, stable aqueous dispersions can be used in mechanical filling and bonding, as well as in applications using chemical binders or fibrillated fibers for the compacted form of thermally bonded microparticles and the incorporation of solution-treated polymers into form factors.

[0077] The P-CDP materials of this disclosure can also be prepared on a support material (or “substrate”) and can be covalently, adhesively, or mechanically bonded to the support, for example, a fibrous substrate. The support material can be any material having one or more groups (e.g., hydroxyl or amino, thiol, or phosphine, or other groups described herein) that can form interactions (e.g., covalent or mechanical) with the crosslinking agent or cyclodextrin. For example, one end of the crosslinking agent (e.g., the linking group of formula (I), (II), and / or (III)) is covalently bonded to the substrate material, and the other end of the crosslinking agent is covalently bonded to a reaction center on a cyclodextrin glucose unit or modified cyclodextrin (e.g., an acid halide or activated ester bonded to the cyclodextrin). It is desirable that the support material is insoluble under the conditions of use, for example in an aqueous medium (to the extent that it is observable by visual inspection, gravimetric measurement, or spectroscopy). Examples of supporting materials include microcrystalline cellulose, cellulose nanocrystals, polymer materials (e.g., acrylate materials, methacrylate materials, styrene materials (e.g., polystyrene), polyester materials, nylon materials, and combinations thereof), or inorganic materials (e.g., silicates, silicones, alumina, titania, zirconia, and metal oxides such as hafnia, etc.) This includes, but is not limited to, combinations thereof. In various examples, the polymer material is a homopolymer, copolymer, or resin (e.g., a resin containing a polymer material). The support material may be hydroxyl or amino-containing polymer beads or irregular particles. The support material may be in the form of fibers (e.g., pulp, short cuts, staple fibers, and continuous filaments), fiber bundles (e.g., yarn (both spun and continuous filaments)), fiber mats (e.g., nonwovens (both staple and continuous filaments)), fabrics (e.g., knits, woven fabrics, nonwovens), membranes (e.g., films, helical windings, and hollow fibers), cloth, fine particles (e.g., powder), or solid surfaces. In some embodiments, the fibrous substrate is a cellulose substrate. The cellulose substrate may include cellulose derived from plant sources such as wood pulp (e.g., paper or paper fibers), modified cellulose systems such as cotton, regenerated cellulose, cellulose esters and / or ethers, starch, polyvinyl alcohol and its derivatives, or any suitable form of cellulose. The cellulose substrate can be in the form of a cloth, such as a woven or nonwoven fabric, or as fibers, a film, or any other suitable shape, which provides particularly high surface area or porosity. In certain embodiments, the P-CDP material of the present disclosure is bonded to fibers, such as cellulose fibers, or to a cloth, such as cotton.

[0078] In addition to the substrates described in the previous paragraph, the substrates may include any of the following: polyvinylamine, polyethyleneimine, protein, protein-based fibers (e.g., wool), chitosan and amine-containing cellulose derivatives, polyamide, vinyl chloride, vinyl acetate, polyurethane, melamine, polyimide, polystyrene, polyacrylic, polyamide, acrylate-butadiene styrene (ABS), Valnox, PVC, nylon, EVA, PET, cellulose nitrate, cellulose acetate, mixed cellulose esters, polysulfone, polyethersulfone, polyvinylidene fluoride (PVDF) or polytetrafluoroethylene (PFTE or Teflon R.), polyethylene, polypropylene, polycarbonate, phosphine or thiol functional materials, and silicone or combinations thereof. The substrates may also consist of silicon or silicon oxide, or glass (e.g., as microfiber). Suitable materials further include fabrics or synthetic or natural fiber-based materials. The material may have any form or shape, for example, in the form of a sheet, beads, granules, rod, fiber, foam, or tube, and may be rigid, flexible, or elastic.

[0079] If necessary, the material surface can be activated by any known surface activation technique, including, for example, corona treatment, oxygen plasma, argon plasma, selective plasma bromination, chemical grafting, allyl chemistry, chemical vapor deposition (CVD) of reactive groups, plasma activation, sputter coating, etching, or other known techniques. For example, in the case of glass surfaces, such activation is usually not necessary as such surfaces are considered to be already activated as described herein. The purpose of surface activation is to provide a surface suitable for (direct) covalent bonding of surface-modifying functional groups or primer polymers. The surface can be further functionalized after activation as needed. The purpose of surface functionalization is to provide functional groups suitable for covalent bonding of pre-coated polymers.

[0080] Those skilled in the art will recognize the various possibilities of bonding polymers to activated surfaces as needed. These techniques generally involve the introduction of amino, silane, thiol, hydroxyl, and / or epoxy functional groups to a surface, followed by the bonding of polymers to that surface.

[0081] Functionalization may also involve introducing spacers or linkers to the surface to bond the primer polymer to the surface at a predetermined distance. Suitable spacers include, for example, a table Alkylation can occur by reacting a surface with, for example, an aminoalkylsilane.

[0082] P-CDP can be bonded to a substrate via a linking group of this disclosure (for example, via a hydroxyl or amino group of the linking group). “Linker moiety” refers to an atom interposed between the P-CDP and the substrate. The terms “linker” and “linking moiety” as used herein refer to any portion that connects the substrate and the P-CDP to each other. The linking moiety may be a covalent bond or chemical functional group that directly connects the P-CDP to the substrate. The linking moiety may include a set of covalently bonded atoms and their substituents, collectively referred to as the linking group. In some embodiments, the linking moiety is characterized by a first covalent bond or chemical functional group that bonds the P-CDP to the first end of the linker group, and a second covalent bond or chemical functional group that bonds the second end of the linker group to the substrate. The first and second functional groups may be present independently or inactive, and together with the linker group, are collectively referred to as the linker moiety. The linker moiety is defined by the linking group, the first functional group (if present), and the second functional group (if present). In certain embodiments, the linker portion includes atoms interposed between P-CDP and the substrate, independent of the source of these atoms and the reaction sequence used to synthesize the compound. In some embodiments, the linker portion is an aryl portion as described herein. In some embodiments, the linker has one or more of the following functional groups: polyfunctional isocyanates (e.g., diisocyanates), epoxy, carboxylic acids, esters, activated esters, cyanuryl chloride, cyanuric acid, acid chlorides, halogens, hydroxyls, aminos, thiols, and phosphines.

[0083] In some embodiments, P-CDP is grafted or bound onto microcrystalline cellulose (CMC). CMC is available in a variety of median particle sizes from about 10 to about 500 μm, including about 10 μm, 20 μm, 45 μm, 50 μm, 65 μm, 75 μm, 100 μm, 150 μm, 180 μm, 190 μm, 200 μm, 225 μm, 250 μm, 275 μm, 300 μm, 325 μm, 350 μm, 375 μm, 400 μm, 425 μm, 450 μm, 475 μm, and about 500 μm, and all particle sizes in between. In some embodiments, P-CDP is grafted or bound onto CMC to have a median particle size of about 50 μm. For example, CMC is commercialized as Avicel®. In other embodiments, P-CDP is grafted or bonded onto a non-cellulose polymer substrate described herein, whose surface is treated to generate surface functional groups such as hydroxyl groups, as disclosed herein.

[0084] In some embodiments, the P-CDP-substrate composite (e.g., P-CDP crosslinked with an aryl linker in a formula (I)-CMC substrate composite) has a polymer thickness of about 1 nm to about 2000 nm (i.e., the thickness of the porous P-CDP particles on the surface of the substrate). For example, the P-CDP-substrate composite has a polymer thickness of approximately 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, 1500, 1550, 1600, 1650, 1700, 1750, 1800, 1850, 1900, 1950, and ~2000 nm. In some embodiments, the P-CDP-substrate composite has a polymer thickness of less than 1000 nm. In some embodiments, the P-CDP-substrate composite has a polymer thickness of about 800 nm. As will be immediately apparent to those skilled in the art, having a thinner thickness (e.g., less than 1000 nm) allows for a faster rate of absorption of impurities, such as aqueous impurities.

[0085] In some embodiments, P-CDP-substrate composites (e.g., formula (I)-CMC group) The P-CDP material composite, crosslinked with an aryl linker, has an adsorption capacity of up to 500 mg of impurities per gram of CD. For example, the adsorption capacity is approximately 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 1 The adsorption capacity can range from 70, 175, 180, 185, 190, 195, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490 to approximately 500 mg. In some embodiments, the adsorption capacity is up to approximately 200 mg of contaminants per 1 g of CD. In some embodiments, the contaminants are anionic trace contaminants (e.g., PFAS). In some embodiments, the cyclodextrin is β-cyclodextrin. In some embodiments, the linking group is a linking group of formula (I), (II), and / or (III).

[0086] In some embodiments, the P-CDP-substrate composite (e.g., P-CDP crosslinked with an aryl linker of formula (I)-CMC substrate composite) has an equilibrium adsorption capacity of up to 500 mg of impurities per gram of CD. For example, the equilibrium adsorption capacity is approximately 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 16 The amounts can range from 5, 170, 175, 180, 185, 190, 195, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490 to approximately 500 mg. In some embodiments, the equilibrium adsorption capacity is approximately 200 mg of contaminants per 1 g of CD. In some embodiments, the contaminants are anionic trace contaminants (e.g., PFAS). In some embodiments, the cyclodextrin is β-cyclodextrin. In some embodiments, the linking group is a linking group of formula (I), (II), and / or (III).

[0087] In some embodiments, the P-CDP-substrate complex (e.g., P-CDP crosslinked with an aryl linker of formula (I)-CMC substrate complex) has a relaxation time of less than 2 minutes. As will be recognized by those skilled in the art, processes with longer relaxation times reach equilibrium slowly, while processes with shorter relaxation times adapt to equilibrium quickly. In some embodiments, the contaminant is an anionic trace contaminant (e.g., PFAS). In some embodiments, the cyclodextrin is β-cyclodextrin. In some embodiments, the linking group is a linking group of formula (I), (II), or (III).

[0088] In some embodiments, any of the P-CDP materials disclosed herein are grafted or bonded directly onto the CMC or via linker groups, as defined herein. In some embodiments, the P-CDP is uniformly distributed on the CMC surface. In some embodiments, the linker is an aryl linker of formula (I). In some embodiments, the linker is a linking group of formula (II). In some embodiments, the linker is a linking group of formula (III). In some embodiments, the median particle size is about 50 μm. In some embodiments, the median particle size is about 1 to about 250 μm.

[0089] CMCs are distinguished by their particle shape, which is known to have a particular effect on their flow properties. It is also possible. An unrestricted list of particle shapes includes spherical (rounded shape), rod-shaped, and needle-shaped. Particles can also be described as flat, flat and elongated, and can be characterized by their aspect ratio. In some embodiments, CMCs have a spherical particle shape. In some embodiments, CMCs exist in the form of aggregates of smaller CMC particles. Such CMC aggregates can have particle sizes ranging from 200 μm to about 2 mm. For example, the particle size of a CMC aggregate may be about 200 μm, about 300 μm, about 400 μm, about 500 μm, about 600 μm, about 700 μm, about 800 μm, about 900 μm, about 1 mm, about 1.2 mm, about 1.3 mm, about 1.4 mm, about 1.5 mm, about 1.6 mm, about 1.7 mm, about 1.8 mm, about 1.9 mm, or about 2 mm, encompassing all ranges between these values.

[0090] In some embodiments, P-CDP is grafted or bonded to CMC via a linking group of formula (I). In some embodiments, P-CDP is grafted or bonded to CMC via a linking group of formula (Ia). In some embodiments, P-CDP is grafted or bonded to CMC via a linking group of formula (II). In some embodiments, P-CDP is grafted or bonded to CMC via a linking group of formula (III).

[0091] In some embodiments, the P-CDP of this disclosure is grafted or bonded onto a CMC via aryl linkers, which are uniformly distributed on the CMC crystal. In some embodiments, the median particle size is about 100 nm.

[0092] In addition to the use of CMC as described herein, other possible support materials include activated carbon, graphene oxide, and the materials mentioned above, such as silica and alumina.

[0093] In some embodiments, the supported P-CDP material disclosed herein (e.g., P-CDP crosslinked with aryl linkers of formula (I)-CMC substrate composites) is preferably in the form of particles having a narrow particle size dispersion. In some embodiments, the particle size distribution has a low relative span of about 5 or less, where the relative span is (D 90 -D 10 ) / D 50 Defined by the ratio, D 90 , D 50 , and D 10 These are diameters where 90%, 50%, and 10% of the particles in the distribution have a smaller diameter, respectively. Suitable spans are 5, 4.5, 4, 3.5, 3, 2.5, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or less than or equal to 0.1, and include all ranges between these values.

[0094] In various other embodiments, P-CDP may be grafted or bonded onto cellulose nanocrystals (CNCs). CNCs are crystalline regions of cellulose microfibrils obtained after mechanical, chemical, and enzymatic treatment. Depending on the supplier and preparation method, CNCs are available in lengths ranging from about 1 to 1000 nm and widths ranging from about 3 to 50 nm, encompassing all values ​​between these ranges. For example, CNCs have lengths of approximately 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950 to approximately 1000 nm. The CNC has a width of approximately 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or approximately 50. In some embodiments, the P-CDP-CNC substrate may be 2 to 3 times the size (length and width) of the unbonded CNC. The CNC has a width of approximately 2 to 1 It is further characterized by an aspect ratio value (L / D) in the range of 00 (George, J., et al., Cellulose nanocrystals: synthesis, functional properties, and applications. Nanotechnology, Science and Applications. 2015; 8: 45-54). For example, the aspect ratios of CNC are approximately 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, or 100.

[0095] In some embodiments, P-CDP is grafted or bonded onto a CNC via linking groups of formulas (I), (II), and / or (III) as described herein. In some embodiments, P-CDP is grafted or bonded onto a CMC via linking group of formula (I). In some embodiments, P-CDP is grafted or bonded onto a CMC via linking group of formula (II). In some embodiments, P-CDP is grafted or bonded onto a CMC via linking group of formula (III).

[0096] In some embodiments, P-CDP is grafted or bonded onto the CNC via a linker, which is uniformly distributed on the CNC crystal. In some embodiments, the median grain size is approximately 100 nm.

[0097] CNCs can also be distinguished by their particle shape, which is known to particularly affect their flow properties. A non-limiting list of particle shapes includes spherical (rounded), rod-shaped, and needle-shaped. Particles can also be described as flat, flat and elongated, and can be characterized by their aspect ratio. In some embodiments, CNCs have an aspect ratio between about 5 and about 100. For example, aspect ratios can be about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 to about 100. In some embodiments, the aspect ratio of CNCs is about 20 to 25. In some embodiments, CNCs are needle-shaped. In some embodiments, CNCs exist in the form of aggregates of smaller CNC particles. Such CNC aggregates can have a particle size 5 to 100 times larger than the individual particle size, depending on the size and number of particles constituting the aggregate.

[0098] In some embodiments, the substrate is a fabric or fiber. Accordingly, in some embodiments, the Disclosure provides compositions comprising P-CDP grafted or bonded (e.g., chemically or mechanically) to a fiber. In some embodiments, P-CDP is grafted or bonded onto the fiber via linkers of formulas (I), (II), and / or (III) as described herein. In some embodiments, the fiber is a nonwoven fabric fiber. In some embodiments, the Disclosure provides compositions comprising P-CDP grafted or bonded (e.g., chemically, by adhesion, or mechanically) to a fabric. In some embodiments, P-CDP is grafted or bonded onto the fabric via linkers of formulas (I), (II), or (III).

[0099] Suitable fibers for use include fibers containing any of the polymers disclosed herein, for example, gel-spun ultra-high molecular weight polyethylene fibers (e.g., SPECTRA® fibers sold by Honeywell Advanced Fibers in Morristown, NJ, and DYNEMA® fibers sold by DSM High Performance Fibers Co. in the Netherlands), melt-spun polyethylene fibers (e.g., CERTRAN® fibers sold by Celanese Fibers in Charlotte, NC), and melt-spun nylon fibers (e.g., Wich Fibers made from highly oriented fibers include, but are not limited to, high-toughness nylon 6,6 fibers (sold by Invista in Ita, Kans.), melt-spun polyester fibers (e.g., high-toughness polyethylene terephthalate fibers sold by Invista in Wichita, Kans.), and sintered polyethylene fibers (e.g., TENSYLON® fibers sold by ITS in Charlotte, NC). Suitable fibers also include those made from rigid rod polymers such as lyotropic rigid rod polymers, heterocyclic rigid rod polymers, and thermotropic liquid crystal polymers. Suitable fibers also include those made from regenerated cellulose, including reactive wet-spun viscose rayon (viscose sold by Birla in India or Lenzing in Austria), copper ammonia-based rayon (Cupro® Bemberg sold by Asahi Kasei in Japan), or air gap spun from NMMO solvents (Tencel® sold by Lenzing in Austria). Suitable fibers produced from lyotropic rigid rod polymers include poly(p-phenylene terephthalamide) fibers (e.g., KEVLAR® fibers sold by DuPont in Wilmington, Del. and TWARON® fibers sold by Teijin in Japan) and aramid fibers such as fibers produced from a 1:1 copolymer of 3,4'-diaminodiphenyl ether and p-phenylenediamine (e.g., TECHNORA® fibers sold by Teijin in Japan).Suitable fibers produced from heterocyclic rigid rod polymers such as p-phenylene heterocycles include poly(p-phenylene-2,6-benzobisoxazole) fibers (PBO fibers) (e.g., ZYLON® fibers sold by Toyobo in Japan), poly(p-phenylene-2,6-benzobisthiazole) fibers (PBZT fibers), and poly[2,6-diimidazo[4,5-b:4',5'-e]pyridinylene-1,4-(2,5-dihydroxy)phenylene] fibers (PIPD fibers) (e.g., M5® fibers sold by DuPont in Wilmington, Del.). Suitable fibers produced from thermotropic liquid crystal polymers include poly(6-hydroxy-2-naphthoic acid-co-4-hydroxybenzoic acid) fibers (e.g., VECTRAN® fibers sold by Celanese in Charlotte, NC). Suitable fibers include rayon, polyacrylonitrile (e.g., OPF® fiber sold by Dow, Mich. Midland), and carbon fibers produced by high-temperature thermal decomposition of mesomorphic hydrocarbon tar (e.g., THORNEL® fiber sold by Cytec, SC Greenville). In certain preferred embodiments, the yarns or fibers of the fiber layer include fibers selected from the group consisting of gel-spun ultra-high molecular weight polyethylene fibers, melt-spun polyethylene fibers, melt-spun nylon fibers, melt-spun polyester fibers, sintered polyethylene fibers, aramid fibers, PBO fibers, PBZT fibers, PIPD fibers, poly(6-hydroxy-2-naphthoate-co-4-hydroxybenzoic acid) fibers, carbon fibers, and combinations thereof.

[0100] The P-CDP materials of this disclosure can be bonded to such fibers by adhering them with a suitable binder polymer as described herein, or by functionalizing the surface of the fibers as described herein (e.g., surface oxidation to generate surface hydroxyl groups) to form P-CDP in situ on the fiber surface, or by chemically bonding the appropriately functionalized P-CDP to such fibers directly or indirectly via a linker moiety as described herein.

[0101] The fibers can be converted into nonwovens by different bonding methods (before or after P-CDP bonding). Continuous fibers can be formed as webs using industry-standard spunbond-type techniques, while stapled fibers can be formed as webs using industry-standard carding, airlaid, or wet-laid techniques. Typical bonding methods include calendaring. These methods include (pressure and heat), aeration heating, mechanical entanglement, hydrodynamic entanglement, needle punching, and chemical and / or resin bonding. Calendering, aeration heating, and chemical bonding are preferred methods for bonding starch polymer fibers. Pressurized heating and aeration heating bonding methods require heat-bondable fibers.

[0102] The fibers of the present invention can also be bonded or combined with other synthetic or natural fibers to produce nonwoven fabric products. The synthetic or natural fibers can be blended with each other in the molding process or used in separate layers. Suitable synthetic fibers include fibers made from polypropylene, polyethylene, polyester, polyacrylate, and their copolymers and mixtures. Natural fibers include cellulose fibers and their derivatives. Suitable cellulose fibers include those derived from any tree or plant, including hardwood fibers, softwood fibers, hemp, and cotton. Fibers made by processing natural cellulose sources such as rayon are also included.

[0103] Using the fibers of the present invention, non-woven fabrics in particular can be produced among other suitable articles. Non-woven articles are defined as articles containing more than 15% of a plurality of fibers physically and / or chemically bonded to each other, either continuously or discontinuously. Non-woven fabrics can be combined with additional non-woven fabrics or films to produce laminated products used by themselves or as components in complex combinations of other materials. Preferred articles are disposable non-woven articles. The resulting products find use in filters for air, oil, and water; fabrics such as microfibers or breathable fabrics with improved hygroscopicity, odor absorption, and softness for wearing; structured webs with electrostatic charges for collecting and removing dust and contaminants; fibrous products such as surgical drapes, wound dressings, bandages, and skin patches; fibrous products for absorbing water and oil used for wiping up spilled oil and water. The articles of the present invention may also include disposable non-woven fabrics for sanitary and medical uses for absorbing malodors. Sanitary uses include wipes; diapers, particularly top sheets or back sheets; and feminine pads or products, particularly top sheets.

[0104] The yarns or fibers of the fiber layer can have any suitable weight per unit length (e.g., denier). Typically, the weight per unit length of the fibers is from about 1 to about 50 denier (1 to about 50 g per 9000 meters) per filament. The yarns contain from 10 to about 5000 filaments.

[0105] In some embodiments, the P-CDP is adhesively bonded to a substrate such as a fiber or fabric via a binder. In some embodiments, the P-CDP is coated on a substrate such as a fiber or fabric via a binder. In some embodiments, the P-CDP is bonded or coated via a binder to a substrate such as a fiber or fabric by introducing a surface together with a binder into a stable aqueous dispersion of P-CDP particles. The P-CDP particle dispersion may be from 1 to 50 wt%, and the polymeric binder material may be present in the emulsion or solution at 1 to 50 wt%. For example, the P-CDP particle dispersion may be present at about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or about 50 wt%. The polymeric binder material may be present in the emulsion or solution at about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or about 50 wt%. Further adjuvants are used as trace components by weight to control wetting by the substrate (wetting agent), foaming or defoaming of the solution, hand softener for the substrate, and / or catalyst for curing of the binder can be controlled.

[0106] For example, various coating techniques well known in the art can be applied, such as dipping and pressing, solution casting, foam coating, or spraying the formulated solution onto the target substrate. Substrates include, but are not limited to, woven, knitted or nonwoven fabrics, continuous filament yarns, spun yarns, spun fibers, wood surfaces, and thermoplastic surfaces. In some embodiments, when the formulated solution is applied to the substrate, the combined system is dried to remove the aqueous solvent, at which point a uniform film of P-CDP particles mixed with a polymer binder is present. During the drying process, the binder material, which exists as an emulsion polymer, flows together to form a continuous phase. Depending on the choice of binder, the P-CDP particles are held in place by mechanical means or by adhesion to the binder continuous phase alone, or further covalent bonds may exist if a curable binder is selected. Such covalent bonds can extend the underlying substrate, further enhancing the durability of the P-CDP particle coating.

[0107] As will be immediately apparent to those skilled in the art, the resulting P-CDP particle film conforms to the shape of the underlying substrate, is durable against physical abrasion and washing, and can be used to unfold articles. Furthermore, when the P-CDP particles can access the aqueous or gas phase within the coating, they exhibit the same selective and high-affinity small molecule adsorption properties as monolithic particles. Such form factors can be converted into filter cartridges, pleated filters, nonwoven needle-punched filters, sanitary nonwovens, and clothing.

[0108] Various binders well known to those skilled in the art may be used in connection with this disclosure, including any of those disclosed in U.S. Patent Application Publication No. 2014 / 0178457A1, which is incorporated herein by reference in its entirety. Suitable binders include, but are not limited to, latex binders, isocyanate binders (e.g., blocked isocyanate binders), acrylic binders (e.g., nonionic acrylic binders), polyurethane binders (e.g., aliphatic polyurethane binders and polyether-based polyurethane binders), epoxy binders, urea / formaldehyde resins, melamine / formaldehyde resins, polyvinyl alcohol (PvOH) resins (disclosed in U.S. Patent No. 5,496,649, which is incorporated herein by reference in its entirety) and their crosslinked forms, polyethylene vinyl alcohol (EvOH) and its crosslinked forms, polyethylene vinyl acetate (EVA), starch and starch derivatives, cellulose ether derivatives, and cellulose ester derivatives. Small molecules, polymers, or inorganic crosslinking agents, including formaldehyde, glyoxal, diisocyanates, diexoxides, and / or sodium tetraborate, and combinations thereof, can be further used.

[0109] In some embodiments, P-CDP particles are mechanically bonded to a surface such as fibrillated fibers. These fibrillated fibers are used to form a high-surface-area extended network capable of coating and trapping particulate matter. Fibers such as fibrillated polyolefins (e.g., Mitsui Fybrel®), fibrillated regenerated cellulose (e.g., Lenzing Tencel®), and fibrillated acrylics (e.g., Sterling Fibers CFF®) are deployed in a wet-laid process to produce specialty papers with excellent mechanical properties, good wet strength, and the ability to retain particulate matter (U.S. Patent No. 4,565,727, as fully incorporated herein by reference) (e.g., Onxy Specialty Papers, Helsa Corporation). More specifically, powdered activated carbon particles larger than 5 microns in diameter are loaded onto specialty carbon papers deployed in liquid and vapor filtration applications such as point-of-use water filters or cabin air filters.

[0110] In the papermaking process, a mixture of short-cut fibers (such as wood pulp, polyester, nylon, or polyolefin), fibrillated fibers (such as Fybrel®, Tencel®, or CFF®), and particulate powder materials is mixed (e.g., under high shear). This mixture can then be rapidly passed through a nonwoven mesh or screen to deposit a wet-laid nonwoven web. The web is then dried (e.g., on a hot air oven or heated roll) to remove the water carrier. Further bonding can be performed using a cold or hot calender on either a flat format or a patterned roll to produce bonded specialty paper. The particulate powder used can be a dispersion of P-CDP fine particles of a specified particle size. The particle size can be set using the previously defined grinding and milling techniques. The amount of fine particles loaded into the finished nonwoven may reach 60% by weight. The fine particles can be used alone or blended with other fine particles, such as powdered activated carbon. Further chemical binders, such as those described herein, may be used to modify or enhance the properties of the paper and are applied in a manner understandable to those skilled in the art.

[0111] The resulting powder-filled paper is suitable for high loads of P-CDP adsorbent particles in a paper filter form factor that is convenient for water and / or air filtration. The paper can be used in a flat form, cut into various shapes, or pleated and bonded into filter cartridges.

[0112] In some embodiments, P-CDP particles are mechanically entangled in a yarn (e.g., a continuous filament yarn). As will be immediately apparent to those skilled in the art, a special subset of yarn finishes can, depending on the circumstances, mechanically bind particulate matter within a continuous filament yarn. If the yarn (e.g., a continuous filament) is composed of multiple filaments of a common synthetic polymer such as polyethylene terephthalate (PET) or polyamide (nylon 6 or nylon 6,6) that is prone to microfibrillation on the surface of each filament, then particulate matter can be incorporated into the yarn bundle. The P-CDP particles of this disclosure can be incorporated into yarn in a variety of ways. One non-limiting example is to apply a dispersion of the P-CDP particles of interest to a yarn bundle in motion during a false-twist process by dip coating or oil roll application. In this process, each filament is mechanically separated by twisting it first in one direction and then in the opposite direction. After the initial twist, each filament is individualized, creating voids within the yarn bundle. The dispersion is applied at this point in the process, after which the bundle is twisted back to a standard orientation, and the yarn is heated to dry the solution. This process allows for the application of dispersed particles into the yarn bundle, which are held in place by the continuous filaments and microfibrils arising from the continuous filament surface. Such approaches have been used to apply various micron-sized particles, including microcapsules (U.S. Patent Application Publication 2005 / 0262646A1, which is fully incorporated herein), metallic silver nanoparticles (U.S. Patent Application Publication 2015 / 0361595A1, which is fully incorporated herein), to continuous filament yarns, and to apply other functional particles (U.S. Patent Application Publication 2006 / 0067965A1, which is fully incorporated herein) to bundles of synthetic fibers. These processed, particle-filled yarns can then be processed by common means to form knitted and woven fabrics for use in clothing, upholstery, medical, display, or other applications.

[0113] In some embodiments, P-CDP particles are incorporated into a compacted form of heat-bonded fine particles. The common form factor of powder absorbent materials is the heat-bonded compacted form. Such a form factor can contain up to 95% by weight of P-CDP particles, and may include inorganic materials such as fibrilized fibers (Fybrel®, Tencel®, or CFF®), possibly attapulgite clay, and finally organically bonded materials. By adding additive materials (most commonly cellulose esters and similar derivatives), a porous composite structure with suitable mechanical strength and particulate retention efficiency for medium-pressure filtration applications such as faucet filters and refrigerator filters is formed (see U.S. Patents 5,488,021 and 8,167,141, both of which are incorporated herein by reference in their entirety).

[0114] P-CDP dried particles or dispersions can be used in place of other adsorbents or blended with other adsorbents to form composite adsorbent P-CDP microparticle-containing forms as described above. In such embodiments, each solid dried component can be dry-blended and may optionally include dry P-CDP particles containing or not containing inorganic clay and / or fibrillated fibers, and organic binder powder. When using an aqueous dispersion of P-CDP particles, it can be diluted with water and added to the mixture. Water is added (e.g., 80-150 wt%), and the mixture is blended (e.g., under high shear) to form a plastic material. This material can be molded into the desired form factor and dried and cured at a temperature in the range of 125-250°C. This final form factor provides P-CDP adsorbent particles in a useful form factor common to point-of-use water filters.

[0115] In some embodiments, P-CDP particles are incorporated into a solution-treated polymer form factor. Various means are available for producing filter membrane materials. For example, solution-cast films are used, or hollow fibers of a membrane polymer are extruded, and a condensed film with a controlled pore size is formed by controlled coagulation. In some embodiments, polymers such as cellulose acetate dissolved in a water-miscible organic solvent such as NMP, DMSO, or THF are used. This solution can be cast into a film in a water bath, which causes rapid coagulation of the cellulose acetate polymer and densification of the film. These films can be processed in a roll-to-roll apparatus, wrapping multiple layers to form a helical wound membrane filter for use in microfiltration, ultrafiltration, gasfiltration, or reverse osmosis applications. Common polymers used instead of cellulose acetate include polyamides, polyolefins, polysulfones, polyethersulfones, polyvinylidene fluoride, and similar modified thermoplastics. It is also possible to extrude hollow fibers into an aqueous solution to form membrane fibers known as hollow fiber membranes, which are commonly used in dialysis, reverse osmosis, and desalination applications, by a phase inversion process.

[0116] In some embodiments, P-CDP particulate matter is incorporated into the membrane material to enhance its performance. For example, a small amount of P-CDP particle dispersion can be present in an aqueous coagulation bath, and this particle dispersion is incorporated into the high-density or porous portions of the membrane during the phase inversion process. A second method for incorporating P-CDP particles into a membrane is to incorporate a small amount of well-dispersed particles into an organic solution of the membrane polymer, and the particles are encapsulated in the membrane after coagulation. Each of these methods enables the production of polymer foams filled with P-CDP. In various embodiments such as microfiltration, ultrafiltration, and reverse osmosis, the incorporation of P-CDP particles acts to enhance the removal performance of trace contaminants from the membrane system.

[0117] In some embodiments, P-CDP particles are incorporated into melt-extruded thermoplastics (e.g., fibers and molded parts). Because low polydispersity, small-diameter dry powder P-CDP particle materials are available, this material can be incorporated into melt-processed polymer foams such as fibers and molded parts. Useful common thermoplastics include polyethylene terephthalate, copolyesters, polyolefins, and polyamides. Since typical extrusion temperatures are 250-300°C, stability of the P-CDP particles at these temperatures in air (most preferred) or under an inert atmosphere is required. Using uniscrew or twin-screw extrusion, the powder material is extruded at high temperatures under shear to up to 5 wt percent of thermoplastic plastics. The components are blended and mixed. After proper mixing, each blended component can be extruded through a small circular or other shaped orifice to produce fibers having a linear density of particulate matter ranging from 1 to 20 denier per filament. A common particle added to many thermoplastic fibers is titanium dioxide, which is added to whiten the fibers and reduce their gloss. P-CDP particles are added in the same manner. In the most ideal embodiment, some of the present particles are accessible by the gas or liquid phase, as the P-CDP particles migrate and extrude to the surface of the fibers due to their higher surface energy. In other embodiments, instead of extruding the polymer molten material through a small orifice, plastic parts can also be produced by blow molding or other melt processing methods. These plastic parts also retain P-CDP particles that are activated to extrude to the surface and remove small molecular trace contaminants (e.g., anionic MPs) from the gas and liquid phases.

[0118] The P-CDP of this disclosure can be supported or formed into various shapes (or form factors) suitable for various applications. For example, the P-CDP material of this disclosure may be in the form of a powder or granules, or formed into a disc in a cellulose material such as paper or other nonwoven fabric, or extruded or pressed into various shapes suitable for applications such as filtration, water treatment, sample absorption, etc., as described herein.

[0119] While providing adsorbents in a supported form is not uncommon, it is important that the method used to fix the adsorbent to a substrate or support is robust enough to withstand the conditions of use. Furthermore, the means of attachment to the substrate must not interfere with or inhibit the adsorption mechanism of the adsorbent. Since the adsorbents disclosed herein can be attached to a support as described herein, the resulting performance properties are minimally affected by the attachment method. In various embodiments, the supported polymer materials of the present invention provide at least 50% of the performance properties that would be given by an adsorbent of the same composition (based on an equal amount of adsorbent) prepared without a support material when measured under the same conditions. Thus, for example, a porous material grafted onto microcrystalline cellulose (e.g., P-CDP crosslinked with aryl linkers in a formula (I)-CMC substrate composite) may have at least 50% of one or more of the specific performance properties found in an unsupported porous material tested under the same conditions.

[0120] In some embodiments, the performance characteristic can be the uptake capacity of a specific contaminant (adsorption capacity), which is measured as the number of milligrams of contaminant adsorbed per gram of P-CDP particles under specific conditions. In other embodiments, the performance characteristic is the equilibrium adsorption capacity (q) as defined herein as follows. e ) can be done as follows.

number

[0121] In yet other embodiments, the performance characteristic is the rate at which equilibrium adsorption of contaminants is reached (the equilibrium adsorption rate of a particular adsorbent). This rate can be expressed as the time required for the supported or unsupported P-CDP of the present disclosure to reach equilibrium for a particular adsorbate (or contaminant).

[0122] In yet other embodiments, the performance characteristic is the rate at which competing adsorbents sequester contaminants from one another. Competing adsorbents can be other substances such as unsupported P-CDPs described herein, or activated carbon (powder or granular), ion exchange resins, and specialty resins (e.g., HLB) used in solid phase microextraction.

[0123] For any of these performance characteristics disclosed above, the performance of the supported P-CDPs of the present disclosure is, for example, at least about 50%, 60%, 70%, 80%, 90%, 100%, 120%, 140%, 160%, 180%, 200%, 220%, 240%, 260%, 280%, 300%, 350%, 400%, 450%, 500% or more compared to unsupported P-CDPs of the same composition tested under essentially the same conditions, such as the same contaminant, temperature, pressure, exposure time, etc., including all values, ranges, and sub-ranges between those values.

[0124] The performance characteristics of this disclosure can be measured by a variety of methods that will be immediately apparent to those skilled in the art, for example, based on bisphenol A or PFAS, or another suitable species disclosed herein. For example, the contaminant can be measured at an initial concentration of BPA or another suitable species ranging from 1 ppb (or 1 microgram / L or 5 nM) to 1 ppt (or 1 g / L or 5 mM) in any aqueous sample, including but not limited to drinking water, wastewater, groundwater, aqueous extracts from contaminated soil, landfill leachate, purified water, or other water containing salt or other organic matter. The pH may be in the range of 0 to 14. For example, the pH may be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14, encompassing all ranges between these values. The performance characteristics can be measured in general terms as described herein (e.g., in Examples 1 and 2), with normal variations (such as temperature and pressure) also assumed.

[0125] In some embodiments, the Disclosure provides manufactured articles comprising one or more P-CDPs or one or more P-CDP-substrate composites of the Disclosure.

[0126] In one embodiment, the manufactured article is a protective device. In one embodiment, the manufactured article is clothing. For example, the manufactured article is clothing (e.g., clothing such as a uniform at least partially coated with a porous polymer material or composition) containing one or more P-CDPs or one or more P-CDP-based composites of the Disclosure. In another example, the article is a filter material containing one or more P-CDPs or one or more P-CDP-based composites of the Disclosure. The filter material can be used as a gas mask filter. In one embodiment, the article is a gas mask containing the filter material. In some embodiments, the article is an extraction device.

[0127] In another embodiment, the article is a solid-phase microphase (SPME) extraction apparatus comprising one or more P-CDPs or one or more P-CDP-substrate composites of the present disclosure, wherein the P-CDP or P-CDP-substrate composite is the extraction phase of the apparatus.

[0128] In another embodiment, the article is an apparatus for solid-phase extraction of polar and semi-polar organic molecules. The apparatus comprises one or more P-CDPs or one or more P-CDP-substrate composites of the present disclosure, instead of an HLB medium (a balanced hydrophilic / lipophilic medium). The performance of the article comprising one or more P-CDPs or one or more P-CDP-substrate composites is superior to that of an HLB medium.

[0129] In another embodiment, the article is a device for liquid filtration of polar and semi-polar organic molecules. The device comprises one or more P-CDPs of the present disclosure or one or more P-CDP-substrate composites bonded within a fibrous web (disclosed in U.S. Patent No. 7,655,112, which is herein by reference in its entirety). Other embodiments include a device comprising P-CDP powder fused via a thermoplastic binder polymer to form a porous monolithic filter medium. (Disclosed in U.S. Patent No. 4,753,728, which is incorporated herein by reference in its entirety).

[0130] The P-CDP materials of this disclosure, in various forms and form factors disclosed herein (including supported and unsupported P-CDP materials), can be used in any application where it is desirable to separate compounds (e.g., anionic or cationic MPs) from fluids (gases such as air, liquids such as water, aqueous beverages, and bodily fluids). P-CDP materials can be used to “capture” or adsorb species of interest for further analysis or quantification (e.g., in the analytical testing of environmental pollutants in air or water), to separate mixtures (e.g., in chromatographic separation), or to separate desirable or valuable species present in dilute forms in a fluid. In some embodiments, the P-CDP materials of this disclosure can be used to purify fluids (e.g., by removing undesirable or harmful impurities) or to isolate desired compounds from mixtures or diluted fluid solutions.

[0131] In some embodiments, the Disclosure provides a method for removing one or more compounds (e.g., anionic MPs) from a fluid sample or for determining the presence or absence of one or more compounds in a fluid sample, comprising: a) contacting a sample with a porous polymer material of the Disclosure or a supported porous polymer material of the Disclosure over an incubation period; b) separating the porous polymer material or the supported porous polymer material from the sample after the incubation period; c) heating the porous polymer material or the supported porous polymer material separated in step b) or contacting the porous polymer material or the supported porous polymer material separated in step b) with a solvent to release at least a portion of the compounds from the porous polymer material or the supported porous polymer material; d1) optionally isolating at least a portion of the compounds released in step c), or d2) determining the presence or absence of the compounds released in step c), wherein the presence of one or more compounds correlates with the presence of one or more compounds in a sample. In some embodiments, the one or more cyclodextrin moieties are β-cyclodextrin moieties. In some embodiments, the determination is performed by gas chromatography, liquid chromatography, supercritical fluid chromatography, or mass spectrometry. In some embodiments, the contact is performed by flowing an aqueous phase across, on, around, or through a supported porous polymer material. In some embodiments, the aqueous sample is contacted with the P-CDP-substrate composite under static conditions over an incubation period, and after the incubation period, the aqueous sample is separated from the porous polymer material. In some embodiments, the sample is a food product and the compound is a volatile organic compound. In some embodiments, the aqueous sample is an aqueous extract from drinking water, wastewater, groundwater, contaminated soil, or landfill leachate. In some embodiments, the sample is a perfume or fragrance and the compound is a volatile organic compound. In some embodiments, the compound is an anionic trace contaminant, a heavy metal, and / or a dye.In some embodiments, the compound is an anionic MP such as a PFAS (e.g., polyfluorinated alkyl compounds and / or perfluoroalkyl compounds). In some embodiments, the PFAS is PFOA and / or PFOS.

[0132] In one embodiment, a method is provided for purifying an aqueous sample containing one or more organic compounds, the method comprising contacting the aqueous sample with a porous polymer material of the Disclosure or a supported porous polymer material of the Disclosure, such that, for example, at least 50% to at least 99% of the one or more contaminants bind to one or more cyclodextrin (e.g., β-cyclodextrin) portions of the porous polymer material. For example, the aqueous sample is flowed across, around, or through the porous polymer material. In another example, the aqueous sample is statically... Under certain conditions, the aqueous sample is brought into contact with a porous polymer material or a supported porous polymer material over an incubation period, and after the incubation period, the aqueous sample is separated from the porous polymer material (e.g., by filtration). This method can be used to purify aqueous samples such as drinking water, wastewater, groundwater, aqueous extracts from contaminated soil, and landfill leachates. In some embodiments, the organic compound is an anionic MP such as PFAS.

[0133] In one embodiment, a method for determining the presence or absence of a compound (e.g., anionic MP) in a sample includes: a) contacting the sample with the porous polymer material of the Disclosure or the supported porous polymer material of the Disclosure for an incubation period (e.g., less than 1 minute, less than 5 minutes, or less than 10 minutes); b) separating the composite from a) from the sample; c) heating the composite material from b) or contacting the composite from b) with a solvent (e.g., methanol) so that at least a portion of the compound is released by the porous material; and d) determining the presence or absence of any compound, determining that the presence of one or more compounds correlates with the presence of one or more compounds in the sample, or isolating the compound (e.g., by filtration). For example, the determination (e.g., analysis) is performed by gas chromatography or mass spectrometry. For example, the sample is a food or beverage (e.g., milk, wine, fruit juice (e.g., orange juice, apple juice, and grape juice)), or an alcoholic beverage (e.g., beer and spirits)), and the compound is a volatile organic compound. Porous polymer materials or supported porous polymer materials can be used as the extraction phase in a solid-phase microextraction (SPME) apparatus. In some embodiments, the organic compound is an anionic polymer such as PFAS.

[0134] In one embodiment, a method for removing a compound (e.g., an organic compound) from a sample includes: a) contacting the sample with the porous polymer material of the Disclosure or the supported porous polymer material of the Disclosure over an incubation period so that at least a portion of the compound is sequestrated in the polymer; b) isolating the composite from a) from the sample; c) heating the composite from b) or contacting the composite from b) with a solvent (e.g., methanol) so that at least a portion of the compound is released by the porous polymer material; and d) isolating at least a portion of the compound as necessary. In some embodiments, the compound is an anionic polymer such as PFAS.

[0135] These methods allow various compounds to be handled by the method (e.g., isolation, detection, and / or separation). The compounds may be organic compounds. The compounds may be desired compounds such as flavorings (e.g., compounds that affect the palatability of food) or pharmaceutical compounds (or pharmaceutical intermediates), contaminants (e.g., PCBs, PBAs, etc.), and / or impurities. In some embodiments, the compounds are anionic MPs such as PFAS. In some embodiments, the compounds are gemfibrozil, oxybenzone, diclofenac, ioxinyl, ketoprofen, naproxen, sulfamethoxazole, warfarin, 2,4-dichlorophenoxyacetic acid, clofibric acid, ibuprofen, 2-methyl-4-chlorophenoxyacetic acid, mecoprop, valsartan, perfluorobutanoic acid, perfluorobutanesulfonic acid, perfluoropentanoic acid, perfluoropentanesulfonic acid, perfluorohexanoic acid, perfluorohexanesulfonic acid, An anionic MP selected from the group consisting of perfluoroheptanoic acid, perfluoroheptanesulfonic acid, perfluorooctanoic acid, perfluorooctanesulfonic acid, perfluorononanoic acid, perfluorononanosulfonic acid, perfluorodecanoic acid, perfluorodecanesulfonic acid, perfluoroundecanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorotetradecanoic acid, 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)propanoate, and combinations thereof.

[0136] Cyclodextrins are chiral. In one embodiment, chiral compounds are segregated, detected, and / or isolated. In one embodiment, a chiral column (e.g., a preparative or analytical scale column packed with a chiral porous polymer material or a composition containing a chiral porous polymer material) is used to separate and detect or isolate a single enantiomer of a compound (or to at least significantly concentrate the sample with respect to one of the enantiomers).

[0137] This method allows for the regeneration of porous polymer materials or supported porous polymer materials (for example, for reuse in the method). For example, porous polymer materials can be regenerated by heating and / or exposure to a solvent (e.g., alcohols such as methanol or ethanol, and aqueous mixtures thereof).

[0138] The following embodiments are provided to illustrate the present disclosure and should not be construed as limiting the present disclosure. [Examples]

[0139] Example 1: Synthesis of β-CD-TDI polymer Reagents: β-CD: Wacker, Cavamax W7 (ready to use); Trilen-2,4-diisocyanate (TDI): Sigma Aldrich, 95%, product number T39853; N,N-dimethylformamide (DMF): Fisher Chemical, certified ACS grade, catalog number D119-4; Water: Deionized (DI) water from Milli-Q system.

[0140] Procedure: β-CD (60.0 g, 0.0529 mol, 1 equivalent) was dissolved in 120 mL of DMF in a 500 mL single-necked round-bottom flask using a magnetic stirrer at 400 rpm, and the temperature was set to 80°C. An oil bath equipped with a thermocouple was used for heating. After the β-CD was completely dissolved, TDI (36.8 g, 0.2115 mol, 4 equivalents) was added to the flask at 80°C. Bubbles were observed, presumably due to the presence of water in the reaction medium. Approximately 1 minute after the bubbling stopped, the flask was capped with a rubber septum. After 3 hours, the reaction was stopped by adding 30 mL of methanol and halting the heating. The resulting viscous, clear solution was precipitated in 1.2 L of methanol to obtain a white powder product. After stirring for 1 hour, the crude product was filtered under vacuum using a Buchner funnel. The filtered polymer powder was returned to a 2 L beaker and washed again with 1.5 L of deionized water twice and 1.2 L of methanol once. The washing time during each cycle was 1 hour. After final filtration, the wet solid product was transferred to an evaporating dish and placed in a vacuum oven at 80°C to obtain 72.6 g of dry polymer. It was observed that starting with a TDI of 6 equivalents or more resulted in a hard gel that was difficult to work up. In contrast, TDI:CD ratios in the range of 2:1 to 5:1 yielded powder material when the reaction with methanol was stopped (Table 1). These polymers are soluble in various solvents such as DMF, but not in water. For a detailed comparison of the polymers in Table 1, please refer to Figure 5. [Table 1]

[0141] Optimization experiment of β-CD-TDI

[0142] The β-CD-TDI polymer was further optimized by examining the solubility of β-CD (both as is and dried) in ordinary DMF and anhydrous DMF, and the results are shown in Table 2. As is, β-CD has a water content in the range of 12-14%. [Table 2]

[0143] As shown in Table 2, the solubility of β-CD is greatly affected by its water content. Therefore, when using dry β-CD, polymerization can only be carried out at an initial concentration that will affect the reaction yield. In contrast, since DMF has a low water content, it has little effect on solubility, and it is recommended to use regular DMF in the reaction. A comparison of β-CD-TDI polymers produced in small and large batches is shown in Table 3 below. [Table 3]

[0144] It has long been understood that the use of dry β-CD and anhydrous solvents is important for producing polyurethane-type CD polymers. However, as described herein, when "hydrated" solvents (also called "ordinary" solvents) such as DMF and / or as-is β-CD are used, the resulting polymers are structurally different from those described in the literature and are more effective in sequestering PFAS. It was unexpectedly discovered that when using hydrated / ordinary solvents, partial isocyanate reduction occurs, as shown in Scheme 1 for TDI below. Scheme 1: Effect of water on the isocyanate group of TDI. [ka]

[0145] The presence of amine groups in the polymerization reaction is thought to lead to the formation of urea bonds in addition to urethane bonds resulting from crosslinking between β-CD and TDI under anhydrous conditions (e.g., completely anhydrous conditions). Furthermore, the presence of free amines in the β-CD-TDI polymer is thought to contribute to the removal of PFAS. The high amine and urea content structurally differs from conventional technologies and provides a polymer that is more advantageous in removing anionic trace contaminants (e.g., PFAS).

[0146] Elemental analysis data shows that the final CD:TDI ratio is 1:8–1:10 when using a 1:4 supply ratio, suggesting the presence of excess TDI units on the cyclodextrin. Furthermore, 1 ¹H NMR spectroscopy revealed the presence of -CH3 protons derived from amine-functionalized phenyl units (Figure 3). The amine group can be quantified using the approximately 1.9 ppm -CH3 peak derived from the amine-containing TDI units. The ratio of the integral of each -CH3 peak to the total integral gives the percentage of TDI containing amine. Since the absolute TDI density can be calculated from elemental analysis data, the concentration of amine groups (mmol / g) in the polymer can be calculated by correlating the NMR and EA data. See Table 4. The β-CD-TDI polymer was further determined to be positive in the chloranil test, further confirming the presence of amine. [Table 4]

[0147] Amine-containing β-CD-TDI polymer was used in a panel of 12 types of PFAS (Figure 1) and P Further testing was conducted on a two-component mixture of FOA and PFOS (Figure 2). The polymer (SL-1-010A) prepared with 4 equivalents of TDI showed a 70% removal rate of PFOA and an excellent PFOS removal rate (96%) in panel testing in just 30 minutes, reaching nearly 90% PFOA and 100% PFOS removal rates after 48 hours. Similar removal performance was observed when testing a two-component mixture of PFOA and PFOS.

[0148] Example 2: Synthesis of β-CD-isocyanate polymer and PFAS removal activity Following the general procedure outlined in Example 1, β-CD-isocyanate polymers obtained from 4,4'-MDI were synthesized and tested for their ability to remove PFAS.

[0149] Each polymer in Table 5 was tested for its ability to remove PFAS. All experiments were performed using 1000 ng / L and 10 mg / L adsorbents for each of the 12 PFAS species. Control experiments were performed without adsorbent. These experiments were performed in triple replication. Samples were collected at 0, 0.5, 9, and 48 hours. Figure 1 shows the results at 0.5 and 48 hours, where polymers prepared from 4,4'-MDI and 2,4-TDI were particularly effective in sequestering PFAS. A faster removal rate was observed with the TDI polymer (SL-1-010A), but the MDI polymer (SL-0420-3) also showed good removal performance over 48 hours. Polymers obtained from 6 equivalents of TDI and MDI did not show good removal rates for either PFOA or PFOS, which is thought to be due to the formation of a hard gel during synthesis, preventing access to the binding sites within the particles. [Table 5]

[0150] Example 3: Synthesis of choline chloride-modified β-CD-TFN polymer and PFAS scavenging activity In this example, a positive charge was imparted to each CD polymer to enhance its binding affinity to anionic PFAS. While not constrained by specific theories, it is believed that the presence of phenolic groups generated by side reactions during polymerization imparts an anionic charge to the polymer, reducing its uptake of PFOA and PFOS. This effect was experimentally observed with another polymer formulation, TFN-CDP, which exhibited excellent removal performance for a wide range of trace contaminants, excluding negatively charged contaminants including PFAS. TFN-CDP can be produced relatively on a large scale using tetrafluoroterephthalonitrile (TFN) as a crosslinking agent. Therefore, it was desirable to modify the PFAS adsorption properties by incorporating a positive charge into the polymer backbone. In this example, choline chloride (a quaternary ammonium salt with a hydroxyl group) was selected as an additive to the polymerization reaction of TFN-CDP. Choline chloride can react with TFN, similar to β-CD, and is therefore incorporated into the polymer. This polymer will be referred to as TFN-CDP+ below (Scheme 2). Scheme 2: Overview of the synthesis of choline chloride-modified β-CD-TFN polymer [ka] [Table 6] [Table 7] [Table 8]

[0151] Before measuring the PFAS removal rate, we compared the uptake rates of BPA (neutral molecule) and methyl orange (MO, negatively charged dye molecule) of TFN-CDP and TFN-CDP+. While the BPA uptake rate remained unaffected, the MO uptake rate improved significantly, rising from approximately 30% for TFN-CDP to over 99% for TFN-CDP+. As expected, the TFN-CDP+ polymer showed significantly lower affinity for positively charged molecules such as methylene blue compared to TFN-CDP (Table 9, Figure 7). Based on this preliminary data, we tested TFN-CDP+ for the removal rate of PFOA and PFOS at environmentally relevant concentrations. [Table 9]

[0152] While further experiments are needed to fully characterize the adsorption mechanism, this approach allows for (1) simultaneous utilization of dual binding mechanisms (a β-CD inclusion complex and ionic interactions) within a single material, and (2) enhanced binding affinity of the inclusion complex due to the presence of positive charges near the CD cavity. Furthermore, TFN-CDP+ is synthesized in a single step, and the amount of positive charge incorporated can be easily altered by changing the amount of choline chloride used in the reaction.

[0153] Experimental procedure: β-CD (1 g, 0.881 mmol), TFN (1.06 g, 5.286 mmol), K2CO3 (2.44 g, 17.621 mmol), choline chloride (0.37 g, 2.643 mmol), and 5.4 mL of H2O / DMSO (2:3, v / v) were added to a 20 mL scintillation vial equipped with a magnetic stirrer. The mixture was stirred at 60°C for 20 hours. An additional solvent (1 mL) was added after the first hour of stirring. After 20 hours, 10 mL of water was added, and the polymer was stirred for 30 minutes to disperse. After filtration, the crude product was transferred to a centrifuge tube. The sample was washed three times with hot methanol (approximately 40 mL) (30 minutes in each cycle). After decanting the methanol, deionized water (approximately 30 mL) was added. 1 M HCl was added dropwise while stirring the sample until the pH stabilized between 3 and 4. The crude product was washed two more times with high-temperature methanol (approximately 40 mL). The final methanol wash was filtered under vacuum, and the product was dried overnight at 80°C.

[0154] PFOA and PFOS Removal Performance Testing - PFAS adsorption experiments were conducted to measure the removal performance of different TFN-CDP+ polymers. To facilitate the screening process of numerous polymer formulations, adsorption rate tests were performed using a mixture of 12 different PFAS in nanopure water. Understanding the adsorption rate is essential as it reveals information about the adsorbent dosage and required contact time related to the processing process. This panel experiment not only provides insights into the uptake rates of PFOA and PFOS but also enables the evaluation of performance against other PFAS such as GenX and short-chain and long-chain PFAS, thereby allowing for the determination of the broad PFAS removal capabilities of these polymers. The results summarized in Figure 1 show the removal rate (%) of each PFAS at contact times of 30 minutes and 48 hours. These experiments were performed in triplicate using approximately 1 ppb of each of the 12 different PFAS in nanopure water with a polymer load of 10 mg / L. A control experiment without adsorbent was also performed to correct the reported removal rate (%) for the amount of loss observed in the control experiment. All polymers were sieved through a 230-mesh sieve.

[0155] Notably, two derivatives of TFN-CDP+ (i.e., MB-1-036 and MB-1-037, prepared from 3 equivalents and 6 equivalents of choline chloride, respectively) exhibited the best removal performance among all polymers tested, with almost complete removal of all PFAS in the panel. MB-1-037 showed effective removal of GenX and short-chain PFAS in addition to PFOA and PFOS over 30 minutes, which is likely due to its high quaternary ammonium loading capacity (Figure 2).

[0156] After an initial screening under panel experiments, polymers were selected by narrowing down the removal rate evaluation using a two-component mixture of PFOA and PFOS (Table 10). In this particular task, all adsorption experiments were performed using 0.5 ppb of PFOA and 1 ppb of PFOS with a polymer load of 10 mg / L. A control experiment without adsorbent was performed, and all measurements were tripled. Samples from each solution were taken for analysis at predetermined time points of 0, 0.5, 2, 4, 8, and 24 hours. The polymers selected for these measurements were SL-1-010A(TDI), MB-1-036(TFN+CC), and MB-1-037(TFN+CC). All polymers tested showed high PFOS removal rates over 24 hours, however, SL-1-010A(TDI) and two TFN-CDP+ derivatives showed high removal (over 90%) in only 30 minutes. Regarding PFOA removal, while SL-1-010A(TDI) showed similar performance to the panel experiment, MB-1-036 and MB-1-037 outperformed the other two polymers in both kinetics and 24-hour removal capacity.

[0157] [Table 10]

[0158] Experiment on adsorption of trace pollutants

[0159] β-CD is known to form stable inclusion complexes with trace contaminants. BPA and MO were selected as model compounds to test the uptake of neutral and negatively charged trace contaminants, respectively, in order to understand the adsorption mechanism in choline chloride-modified TFN-CDP polymers. Furthermore, by fitting the trace contaminant adsorption data as a function of concentration to the Langmuir model (Equations 1 and 2), the thermodynamic parameters of the tested material can be determined.

[0160] A single-site Langmuir model assuming a homogeneous adsorption surface is given as follows:

number

number

[0161] In the case of choline chloride-modified TFN-CDP polymers, the maximum MO capacity (q) of the polymer prepared using 1.5 equivalents and 3.0 equivalents of choline chloride, respectively, for the first adsorption site is... max,1 The values ​​were 46.6 and 78.8 mg / g (Table 11, Figure 8). Second adsorption site (q max,2 ) represents the maximum uptake capacity of 37.3 and 33.0 mg / g, and these are both the maximum capacity of unmodified TFN-CDP (q max This value is extremely close to 37.6 mg / g. This data, as well as K L and K L,2 The similarity between the values ​​suggests that the second adsorption site of the choline chloride-modified TFN-CDP polymer is related to MO adsorption into the CD cavity. L,1 and K L,2 The comparison of the values ​​also indicates a significantly stronger primary adsorption site, which is thought to be due to the interaction between the anionic MO molecule and the quaternary ammonium site. When the BPA adsorption data was fitted using a single-site Langmuir model, similar K values ​​were observed for all three polymers. L The values ​​were determined, indicating the presence of similar adsorption sites for neutral molecules. The maximum BPA capacities of the two choline chloride-modified TFN-CDP polymers were 112.1 and 100.1 mg / g, respectively, while the capacity of unmodified TFN-CDP was 106.1 mg / g (Table 11, Figure 9). Notably, these saturated uptake values ​​are in good agreement with the CD site density of these polymers. This observation also suggests that BPA adsorption occurs within the CD cavities.

[0162] [Table 11]

[0163] Example 4: Synthesis of choline chloride-modified β-CD-TDI polymer and PFAS scavenging activity β-CD (2 g, 1.76 mmol, 1 equivalent) was dissolved in 5 mL of DMF in a 20 mL scintillation vial equipped with a magnetic stirrer bar at a stirring speed of 400 rpm and a temperature of 80°C. 4 g of choline chloride was dissolved in 10 mL of DMSO at 80°C to a concentration of 0.4 g / mL. Choline chloride solutions of various stoichiometric ratios ((0.3075 mL, 0.1230 g, 0.5 equivalent), (0.6150 mL, 0.2460 g, 1 equivalent), (0.9225 mL, 0.369 g, 1.5 equivalent), or (1.2300 mL, 0.492 g, 2 equivalents)) were added to the β-CD solution at 80°C. After mixing at 80°C for 5 minutes, toluene diisocyanate (2,4-TDI, 1.8417 g, 10.57 mmol, 6 equivalents) was added. Bubbles, thought to be caused by moisture in the reaction system, were observed after the addition of diisocyanate. The vial was capped approximately 1 minute after the bubbles subsided. After 3 hours, the reaction was stopped by adding 10 mL of methanol and halting the heating. After methanol addition, a white powder product precipitated. The mixture was transferred to a 50 mL polypropylene centrifuge tube. After centrifugation, the solvent was decanted, and the crude product was washed with water (40 mL x 2 times) and methanol (40 mL x 2 times). In each washing cycle, the mixture was stirred for 30 minutes, followed by centrifugation. In the final cycle, the product in methanol was filtered under vacuum and dried overnight at 80°C. Figure 10 shows the choline chloride-modified β-CD-TDI polymer prepared using a molar equivalent ratio of 1:6:1 β-CD:TDI:choline chloride in 5 mL of DMF at 80°C for 3 hours. 1 The 1H NMR spectrum is shown. The presence of urethane and urea groups at concentrations of 7.75–9.5 ppm indicates successful incorporation of choline chloride into the polymer. 1The following chemical shifts are also observed in the 1H NMR spectrum: 6.75–7.75 ppm (proton from the aromatic ring of TDI); 5.5–6 ppm (proton from the -OH group attached to C2 and C3 of β-CD); 4.8–5 ppm (proton attached to C1 of β-CD); 4.25–4.75 ppm (proton from the -OH group attached to C6 of β-CD); 4.1 ppm (proton from the -O-CH2- group of choline chloride); 3.5–4 ppm (proton attached to C2–C6 of β-CD); 3.3–3.5 ppm (proton from water); 3.1–3.2 ppm (proton from the -CH3 group of choline chloride); 2.5 ppm (DMSO); 1.9–2.1 ppm (proton from the -CH3 group of TDI). Peaks marked with an asterisk are due to residual solvent. Figure 11 shows a comparison between choline chloride-modified β-CD-TDI polymer and β-CD-TDI polymer, with the main difference being a broad peak centered at 3.13 ppm. The sharp peaks at 4.1 ppm and 3.1–3.2 ppm originate from unreacted choline chloride. Figure 12 shows a comparison of three types of choline chloride-modified β-CD-TDI polymers with different choline chloride loadings, supporting the view that the peak intensity increases at 3.13 ppm as the amount of choline chloride increases.

[0164] Following the synthesis procedure outlined above, various polymers were prepared using different stoichiometric equivalents as shown in Table 12. Furthermore, the PFOA incorporation rate of the polymers was tested. These results indicate that by incorporating choline chloride into the β-CD-TDI polymer, the cation charge can be controlled while adding the polymer, increasing the PFOA incorporation rate from 70% to 99% compared to the SL-1-010A polymer (Table 12). See also Figure 13.

[0165] [Table 12]

[0166] Equal portions Although the present invention has been described above in relation to the specific embodiments described above, many alternatives, modifications, and other variations will be apparent to those skilled in the art. All such alternatives, modifications, and variations are intended to be within the spirit and scope of the present invention. References (1)Richardson,SD;Ternes,TAAnal.Chem.2018,90,398-428. (2)Carpenter,CMG;Helbling,DEEnviron.Sci.Technol.2018,52,6187-6196. (3)Barry,V.Winquist,A.Steenland,K.Environ.Health Perspect.2013,121,1313-1318. (4)Gallo, V.;Leonardi,G.;Genser,B.;Lopez-Espinosa,M.-J.;Frisbee,SJ;Karlsson,L.;Ducatman,AM;Fletcher,T.Environ.Health Perspect.2012,120,655-660. (5)Melzer,D.;Rice,N.;Depledge,MH;Henley,WE;Galloway,TSEnviron.Health Perspect.2010,118,686-692. (6) DeWitt, JCDietert, RR, Ed.;Molecular and Integrative Toxicology;Springer International Publishing: Cham,2015. (7)Diamanti-Kandarakis,E.;Bourguignon,J.-P.;Giudice,LC;Hauser,R.;Prins,GS;Soto,AM;Zoeller,RT;Gore,ACEndocr.Rev.2009,30,293-342. (8)Vajda,AM;Barber,LB;Gray,JL;Lopez,EM;Woodling,JD;Norris,DOEnviron.Sci.Technol.2008,42,3407-3414. (9)Tetreault,GR;Bennett,CJ;Shires,K.;Knight,B.;Servos,MR;McMaster,MEAquat.Toxicol.2011,104,278-290. (10)Gagne,F.;Bouchard,B.;Andre,C.;Farcy,E.;Fournier,M.Comp.Biochem.Physiol.- C Toxicol.Pharmacol.2011,153,99-106. (11)Alsbaiee,A.;Smith,BJ;Xiao,L.;Ling,Y.;Helbling,DE;Dichtel,WRNature 2016,529,190-194. (12)Alzate-Sanchez,DM;Smith,BJ;Alsbaiee,A.;Hinestroza,JP;Dichtel,WRChem.Mater.2016,28,8340-8346. (13)Ling,Y.;Klemes,MJ;Xiao,L.;Alsbaiee,A.;Dichtel,WR;Helbling,DEEnviron.Sci.Technol.2017,51,7590-7598. (14)Xiao,L.;Ling,Y.;Alsbaiee,A.;Li,C.;Helbling,DE;Dichtel,WRJAm.Chem.Soc.2017,139,7689-7692. (15)Ji,W.;Xiao,L.;Ling,Y.;Ching,C.;Matsumoto,M.;Bisbey,RP;Helbling,DE;Dichtel,WRJAm.Chem.Soc.2018,140,12677-12681. (16)Klemes,M.J.;Ling,Y.;Chiapasco,M.;Alsbaiee,A.;Helbling,D.E.;Dichtel,W.R.Chem.Sci.2018,9,8883-8889. (17)Li,C.;Klemes,M.J.;Dichtel,W.R.;Helbling,D.E.J.Chromatogr.A 2018,1541,52-56. (18) D’Agostino,L.A.;Mabury,S.A.Env iron.Sci.Technol.2017,51,13603-13613. (19)Barzen-Hanson,K.A.;Roberts,S.C.;Choyke,S.;Oetjen,K.;McAlees,A.;Riddell,N.;McCrindle,R.;Ferguson,P.L.;Higgins,C.P.;Field,J.A.Environ.Sci.Technol.2017,51,2047-2057. (20)Breysse,P.N.U.S Departement of Health and Human Services: Agency for Toxic Substances and Disease Registry: Toxicological profile for Perfluoroalkyls.2018. (21)Hu,X.C.;Andrews,D.Q.;Lindstrom,A.B.;Bruton,T.A.;Schaider,L.A.;Grandjean,P.;Lohmann,R.;Carignan,C.C.;Blum,A.;Balan,S.A.;et al.Environ.Sci.Technol.Lett.2016,3,344-350. (22)Kannan,K.;Corsolini,S.;Falandysz,J.;Fillmann,G.;Kumar,KS;Loganathan,BG;Mohd,MA;Olivero,J.;Van Wouwe,N.;Yang,JH;et al.Environ.Sci.Technol.2004,4948-495. (23)Sun,M.;Arevalo,E.;Strynar,M.;Lindstrom,A.;Richardson,M.;Kearns,B.;Pickett,A.;Smith,J.;Knappe,DRUEnviron.Sci.Technol.Lett.2016,3,415-419. (24)Eschauzier,J.;Beerendonk,E.;Scholte- Veenendaal,P.;De Voogt,P.Environ.Sci.Technol.2012,46,1708-1715. (25)Xiao,L.;Ching,C.;Ling,Y.;Nasiri,M.;Klemes,MJ;Reineke,TM;Helbling,DE;Dichtel,WR(Submitted to Chem.Mater.December 2018) 2019,1-9. (26)Mason,CR;Maynard-Atem,L.;Heard,KWJ;Satilmis,B.;Budd,PM;Friess,K.;Lanc,M.;Bernardo,P.;Clarizia,G.;Jansen,JCMacromolecules 2014,47,1021-1029. (27)Vojkovsk,T.Pept.Res.1995,8,236-237. (28)Marik,J.;Song,A.;Lam,KSTetrahedron Lett.2003,44,4319-4320. (29)Buckley,D.;Henbest,HB;Slade,PJChem.Soc.1957,4891,4891.

[0167] According to a preferred embodiment of the present invention, for example, the following is provided: (Section 1) Equation (I): [ka] A porous polymer material comprising multiple cyclodextrins crosslinked by multiple crosslinks having, During the ceremony, A is an aryl or heteroaryl moiety, Each R 1 These are H, C1-C6 alkyl, C1-C3 haloalkyl, aryl, heteroaryl, -CF3, -SO3H, -CN, -NO2, -NH2, -NCO, -C(O)2R 3 ,-C(O)N(R 3 )2, and -halogens are independently selected from the group, Each R 2 These are independently H, -OH, -O-metal cation, alkyl, aryl, heteroaryl, -SH, -S-metal cation, -S-alkyl, -C(O)2H, or -C(O)NH2. Each R 3 These are independently -H, -C1~C6 alkyl, -C1~C3 haloalkyl, aryl, and -C(O)N(R) a )(R b ), -C(O)R c , -CO2R c , -SO2N(R a )(R b ), or -SOR c And each R a and R b These are independently H or C1-C6 alkyl groups. Each W independently consists of a bond, an alkylene group, an arylene group, a heteroarylene group, -O-arylene-, and -(CH2). a -Ariren-, -SO2-Ariren-, -NH-Ari -Ren-, -S-Arirene-, -O-Heteroarirene-, -(CH2) a-heteroarylene-, -SO2-heteroarylene-, -NH-heteroarylene-, -S-heteroarylene-, -(-O-(CH2) a -) x -,-(-NH-(CH2) a -) x -,-(-S-(CH2) a -) x -, [ka] There, a is between 0 and 100, x is between 1 and 100, and each arylene or heteroarylene moiety may be substituted or unsubstituted. Each Z is either a cationic or anionic moiety. Each L independently consists of -O-, -S-, -N-, substituted or unsubstituted alkylenes of C1-C6, and haloalkylenes of C1-C3. [ka] A connecting part selected from the group consisting of, A' is a covalent bond to A, Z' is a covalent bond to Z, *teeth, [ka] It is a covalent bond to, [ka] These are binding sites to multiple cyclodextrin carbon atoms, x ranges from 0 to 8. y1 is 1 to 4, y2 is between 1 and 4. y3 is between 0 and 4. The aforementioned porous polymer material. (Section 2) The cationic portion is -N(R 3 )3 + , -P(R 3 )3 + , -S(R 3 )2+ , or -heteroaryl + The porous polymer material described in item 1 above. (Section 3) The anionic portion is [ka] And each R 3 However, independently, -H, C1-C6 alkyl, C1-C3 haloalkyl, aryl, -C(O)N(R) a )(R b ), -C(O)R c , -CO2R c , -SO2N(R a )(R b ), or -SOR c And each R a and R b The porous polymer material according to item 1 above, wherein the member is independently H or a C1-C6 alkyl group. (Section 4) Each cationic moiety is -N(R 3 )3 + The porous polymer material described in item 2 above. (Section 5) Each cationic moiety is -N(Me)3 + The porous polymer material described in item 4 above. (Section 6) -WZ, when combined, becomes -O-CH2-CH2-N(Me)3 + A porous polymer material as described in item 5 above, which forms a porous polymer material. (Section 7) A porous polymer material according to any of the preceding items, wherein each L is -O-. (Section 8) A is an aryl and is selected from the group consisting of phenyl, naphthyl, pyridyl, benzofuranil, pyrazinil, pyridadinil, pyrimidinil, triazinil, quinoline, benzoxazole, benzothiazole, 1H-benzimidazole, isoquinoline, quinazoline, quinoxaline, pyrrole, indole, biphenyl, pyrenyl, and anthracenil, as described in any of the preceding items above. (Section 9) A porous polymer material according to any of the preceding items, wherein A is phenyl. (Section 10) A porous polymer material according to any of the preceding items, wherein each cyclodextrin is selected from the group consisting of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and combinations thereof. (Section 11) The porous polymer material according to item 10 above, wherein each cyclodextrin is β-cyclodextrin. (Section 12) Each R 1 A porous polymer material according to any of the preceding items, wherein the polymer is -F, -Me, -CN, or -NH2. (Section 13) A porous polymer material according to any of the preceding items, wherein x is 1 to 4. (Section 14) A porous polymer material as described in any of the preceding items, wherein y1 is 1 to 2. (Section 15) A porous polymer material according to any of the preceding items, wherein y2 is 1 to 2. (Section 16) A porous polymer material as described in any of the preceding items, wherein y3 is 0. (Section 17) The aforementioned bridge is given by formula (II): [ka] It has, During the ceremony, y2 is either 1 or 2. x is either 1 or 2. The porous polymer material described in item 1 above. (Section 18) The porous polymer material described in item 17 above, wherein y2 is 2 and x is 1. (Section 19) The porous polymer material according to item 17 or 18 above, wherein each cyclodextrin is β-cyclodextrin. (Section 20) Formula (III): [ka] (In the formula, one R 4 is -H and one R 4 The porous polymer material described in item 1 above, comprising multiple linkers (where is -Me). (Section 21) The porous polymer material according to item 20 above, wherein each cyclodextrin is β-cyclodextrin. (Section 22) A porous polymer material according to any of the preceding items, wherein the molar ratio of cyclodextrin to a crosslinking agent of formula (I), (II), or (III) is in the range of about 1:1 to about 1:X, where X is three times the average number of glucose subunits in the cyclodextrin. (Section 23) The porous polymer material according to item 23 above, wherein the molar ratio of cyclodextrin to the linking group of formula (I), (II), or (III) is about 1:6, about 1:5, about 1:4, about 1:3, or about 1:2. (Section 24) The aforementioned polymer is approximately 10 m 2 / g~about 2000m 2 Having a surface area of ​​ / g, the preceding item above A porous polymer material as described in any of the following. (Section 25) A supported porous polymer material comprising porous particles fixed to a solid substrate, wherein the porous particles comprise a plurality of cyclodextrin moieties together with a plurality of crosslinks comprising formula (I), (II), or (III). (Section 26) The solid substrate may be microcrystalline cellulose, cellulose nanocrystals, cellulose pulp, acrylate materials, methacrylate materials, styrene materials, polystyrene materials, polyester materials, nylon materials, silicates, silicones, alumina, titania, zirconia, hafnia, hydroxyl-containing polymer beads, hydroxyl-containing irregular particles, amino-containing polymer beads, amino-containing irregular particles, fiber materials, spun yarn, continuous filament yarn, staple nonwoven fabric, continuous filament nonwoven fabric, knitted fabric, woven fabric, nonwoven fabric, film membrane, spiral wound membrane, hollow fiber membrane, cloth membrane, powder, solid surface, polyvinylamine, polyethyleneimine, protein, protein-based fiber, wool, chitosan, amine-containing cellulose derivatives, polyamide, or chloride. Supported porous polymer materials as described in item 25 above, selected from the group consisting of vinyl, vinyl acetate, polyurethane, melamine, polyimide, polyacrylic, polyamide, acrylate butadiene styrene (ABS), Valnox, PVC, nylon, EVA, PET, cellulose nitrate, cellulose acetate, mixed cellulose esters, polysulfone, polyethersulfone, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, polycarbonate, silicon, silicon dioxide, glass, glass microfiber, phosphine-functional materials, thiol-functional materials, fibrillated polypropylene materials, fibrillated regenerated cellulose materials, fibrillated acrylic materials, and combinations thereof. (Section 27) The fibrous material is selected from the group consisting of pulp fibers, short-cut fibers, staple fibers, continuous filament fibers, and cellulose fibers. The supported porous polymer material according to item 26, wherein the cellulose fibers are selected from the group consisting of wood pulp, paper, paper fibers, cotton, regenerated cellulose, cellulose esters, cellulose ethers, starch, polyvinyl alcohol, polyvinylphenol, and derivatives thereof. (Section 28) The supported porous polymer material according to item 26, wherein the substrate is a bead made from microcrystalline cellulose, cellulose nanocrystals, silica, glass, or a synthetic polymer. (Section 29) The porous polymer material according to item 28, wherein the substrate is microcrystalline cellulose. (Section 30) A method for purifying a fluid sample containing one or more contaminants, the method comprising contacting the fluid sample with a porous polymer material according to any of the above sections 1 to 24 or a supported porous polymer material according to the above sections 25 to 29, wherein at least 50% by weight of the total amount of the one or more contaminants in the fluid sample is adsorbed onto the mesoporous polymer material. (Section 31) The method according to item 30, wherein the fluid sample flows across, around, or through the mesoporous polymer material or the supported polymer material. (Section 32) The method according to item 30, wherein the fluid sample is brought into contact with the porous polymer material or the supported polymer material under static conditions for an incubation period, and after the incubation period, the fluid sample is separated from the mesoporous polymer material. (Section 33) The method according to item 30, wherein the fluid sample is drinking water, wastewater, groundwater, an aqueous extract from contaminated soil, or landfill leachate. (Section 34) The method according to item 30, wherein the fluid sample is in the gas phase. (Section 35) The method according to item 34, wherein the fluid sample comprises one or more volatile organic compounds and air. (Section 36) The method according to item 30, wherein the contaminant is one or more of anionic trace contaminants, heavy metals, and / or dyes. (Section 37) The method according to item 36, wherein the contaminant is an anionic trace contaminant. (Section 38) The method according to item 37, wherein the anionic trace contaminant is a polyfluorinated alkyl compound and / or a perfluoroalkyl compound. (Section 39) The method according to item 38, wherein the perfluoroalkyl compound is PFOA and / or PFOS. (Section 40) The method according to item 36 above, wherein the contaminant is a heavy metal. (Section 41) The aforementioned heavy metal is Pb 2+ The method described in item 40 above. (Section 42) A method for removing one or more compounds from a fluid sample or determining the presence or absence of one or more compounds in a fluid sample, comprising: a) contacting a sample with a porous polymer material according to any of the above sections 1 to 24 or a supported porous polymer material according to the above sections 25 to 29 over an incubation period; b) separating the mesoporous polymer material or the supported porous polymer material from the sample after the incubation period; c) heating the mesoporous polymer material or the supported porous polymer material separated in step b) or contacting the mesoporous polymer material or the supported porous polymer material separated in step b) with a solvent to release at least a portion of the compounds from the mesoporous polymer material or the supported porous polymer material; d1) optionally isolating at least a portion of the compounds released in step c), or d2) determining the presence or absence of the compounds released in step c), wherein the presence or absence of one or more compounds correlates with the presence or absence of one or more compounds in the sample. (Section 43) The method according to item 42, wherein the determination is made by gas chromatography, liquid chromatography, supercritical fluid chromatography, or mass spectrometry. (Section 44) The method according to item 42, wherein the sample is a food product and the compound is a volatile organic compound. (Section 45) The method according to item 42, wherein the sample is a perfume or fragrance and the compound is a volatile organic compound. (Section 46) The method according to item 42, wherein the compound is an anionic trace contaminant, a heavy metal, and / or a dye. (Section 47) A manufactured article comprising a porous polymer material as described in any of items 1 to 24 above, or a supported porous polymer material as described in items 25 to 29 above. (Section 48) The article described in item 47 above, which is a protective device. (Section 49) The articles described in item 48 above, which are clothing. (Section 50) The article described in item 43 above, which is a filter material. (Section 51) An extraction device, as described in item 47 above. (Section 52) The article according to item 51, wherein the extraction apparatus is a solid-phase extraction apparatus capable of adsorbing polar and semi-polar organic molecules.

Claims

1. A porous polymer material comprising a plurality of cyclodextrins crosslinked with a plurality of acid chloride-containing crosslinking agents or ester-containing crosslinking agents, wherein one or more of the plurality of cyclodextrins are Equation (I): 【Chemical Formula 66】 Combined with the linker, During the ceremony, A is an aryl or heteroaryl moiety, Each R1 is independently selected from the group consisting of H, C1-C6 alkyl, C1-C3 haloalkyl, aryl, heteroaryl, -CF3, -SO3H, -CN, -NO2, -NH2, -NCO, -C(O)2R3, -C(O)N(R3)2, and -halogens. Each R2 is independently H, -OH, -O-metal cation, alkyl, aryl, heteroaryl, -SH, -S-metal cation, -S-alkyl, -C(O)2H, or -C(O)NH2. Each R3 is independently -H, -C1-C6 alkyl, -C1-C3 haloalkyl, -aryl, -C(O)N(Ra)(Rb), or -SO2N(Ra)(Rb), and each Ra and Rb are independently H or C1-C6 alkyl. Each W is independently bonded to an alkylene group, an arylene group, a heteroarylene group, -O-arylene-, -(CH2)a-arylene-, -SO2-arylene-, -NH-arylene-, -S-arylene-, -O-heteroarylene-, -(CH2)a-heteroarylene-, -SO2-heteroarylene-, -NH-heteroarylene-, -S-heteroarylene-, -(-O-(CH2)a-)x-, -(-NH-(CH2)a-)x-, -(-S-(CH2)a-)x- 【Transformation 67】 where a is between 0 and 100, x is between 1 and 100, and each arylene or heteroarylene moiety may be substituted or unsubstituted. Each Z is either a cationic or anionic moiety. Each L is, 【Transformation 68】 And, A' is a covalent bond to A, Z' is a covalent bond to Z, *teeth, 【Transformation 69】 It is a covalent bond to, 【Transformation 70】 This is a binding site to one of the cyclodextrin carbon atoms among the plurality of cyclodextrins, x is between 0 and 8. y1 is between 1 and 4. y² is between 1 and 4. y3 is between 0 and 4. Porous polymer material.

2. Each Z is an anionic portion, and the anionic portion is 【Chemistry 71】 The porous polymer material according to claim 1.

3. The porous polymer material according to claim 1, wherein each Z is a cationic portion, and the cationic portion is -N(R3)3+, -P(R3)3+, -S(R3)2+, or -heteroaryl+.

4. The porous polymer material according to claim 3, wherein each cationic portion is -N(R3)3+.

5. The porous polymer material according to claim 3, wherein each cationic moiety is -N(Me)3+.

6. The porous polymer material according to claim 1, wherein each cyclodextrin is selected from the group consisting of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and combinations thereof.

7. The porous polymer material according to claim 1, wherein x and y 3 are each 0.

8. The aryl portion is 【Chemistry 72】 And, 【Transformation 73】 The porous polymer material according to claim 1, wherein A represents any of the substituents bonded to A in formula (I).

9. The aryl portion 【Chemistry 74】 The porous polymer material according to claim 8, wherein x and y 3 are each 0.

10. The porous polymer material according to claim 9, wherein each cyclodextrin is β-cyclodextrin.

11. The aryl portion 【Chemistry 75】 The porous polymer material according to claim 8, wherein x and y 3 are each 0.

12. The porous polymer material according to claim 11, wherein each cyclodextrin is β-cyclodextrin.

13. The aryl portion 【Transformation 76】 The porous polymer material according to claim 8, wherein x and y 3 are each 0.

14. The porous polymer material according to claim 13, wherein each cyclodextrin is β-cyclodextrin.

15. The porous polymer material according to claim 1, wherein the porous polymer material has a surface area of ​​10 m² / g to 2000 m² / g.

16. A method for purifying a fluid sample containing one or more contaminants, the method comprising contacting the fluid sample with a porous polymer material according to claim 1, wherein at least 50% by weight of the total amount of the one or more contaminants in the fluid sample is adsorbed onto the porous polymer material.

17. A method for purifying a fluid sample containing one or more contaminants, the method comprising contacting the fluid sample with a porous polymer material according to claim 12, wherein at least 50% by weight of the total amount of the one or more contaminants in the fluid sample is adsorbed onto the porous polymer material.

18. A method for purifying a fluid sample containing one or more contaminants, the method comprising contacting the fluid sample with a porous polymer material according to claim 14, wherein at least 50% by weight of the total amount of the one or more contaminants in the fluid sample is adsorbed onto the porous polymer material.

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